Use of mineral fines to reduce clinker content of cementitious compositions

ABSTRACT

Mineral fines are used to reduce clinker content in concrete, mortar and other cementitious compositions, typically in combination with one or more pozzolanically active SCMs. Mineral fines can replace and/or augment a portion of hydraulic cement binder and/or fine aggregate. Mineral fines can advantageously replace a portion of cement binder and fine aggregate, acting as an intermediate that fills a particle size void between the largest cement particles and smallest fine aggregate particles. Supplemental lime can advantageously maintain or enhance balance of calcium ions in the mix water and/or pore solution. Supplemental sulfate can advantageously address sulfate deficiencies caused by high clinker reduction, use of water reducers and/or superplasticizers, and SCMs containing aluminates. Such systematic approach to beneficially using mineral fines, SCMs, lime, and sulfate addresses many issues and permits high clinker reduction with similar or increased strength.

CROSS-REFERENCE TO RELATED APPLICATION

This Application claims the benefit of U.S. Prov Pat App No. 62/879,705,filed Jul. 29, 2019 and U.S. Prov Pat App No. 62/874,178, filed Jul. 15,2019, and is a continuation-in-part of U.S. patent application Ser. No.16/180,323, filed Nov. 5, 2018, now U.S. Pat. No. 10,737,980, which is acontinuation-in-part of U.S. patent application Ser. No. 16/028,398,filed Jul. 5, 2018, now U.S. Pat. No. 10,730,805, which is acontinuation-in-part of Intl Pat App No PCT/US18/13097, filed Jan. 10,2018, and a continuation-in-part of U.S. patent application Ser. No.15/866,455, filed Jan. 9, 2018, now U.S. Pat. No. 10,131,575, whichclaims the benefit of U.S. Prov Pat App No. 62/522,274, filed Jun. 20,2017, U.S. Prov Pat App No. 62/451,533, filed Jan. 27, 2017, U.S. ProvPat App No. 62/451,484, filed Jan. 27, 2017, and U.S. Prov Pat App No.62/444,736, filed Jan. 10, 2017. The foregoing applications andcorresponding patents are incorporated by reference in their entirety.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The invention is generally in the field of cementitious compositions,hydraulic cements, blended cements, supplementary cementitiousmaterials, mineral fines, performance-enhancing particulate pre-mixes,and methods of manufacture.

2. Relevant Technology

The cement and concrete industry continuously searches for new ways tosubstitute Ordinary Portland Cement (OPC) with alternative materialsthat are cost-effective and have lower carbon footprint. The manufactureof OPC generates enormous quantities of CO₂, representing an estimated5-7% of manmade CO₂. In general, manufacturing a ton of OPC releasesalmost a ton of CO₂ into the atmosphere. With worldwide cementproduction being about 4.2 billion tons per year, the manufacture ofcement creates approximately 4 billion tons of CO₂ per year. Cement isalso the most costly component in concrete (based on unit cost andquantity added). Reducing clinker content and other cementitious bindersis desirable because it reduces production of CO₂ and cost.

Ground granulated blast furnace slag (GGBFS), fly ash, naturalpozzolans, silica fume, and other mineral substitutes (“supplementarycementitious materials” or “SCMs”) have been used as components ofblended cement and/or as partial cement substitutes in concrete. Whenused in blended cement, SCMs are often interground with clinker. Tooffset strength loss, interground blended cements are typically groundmore finely than OPC, which makes them more reactive but candetrimentally increase water demand and concrete durability. There isalso an upper limit to how much clinker can be substituted with SCMsbefore there is serious loss in strength, especially early strength.While SCMs are widely used, a substantial portion of known SCMs,including much of the fly ash produced, are not used but discarded intothe environment or otherwise remain undeveloped. In spite of knownenvironmental and economic benefits in reducing clinker content throughincreased use of SCM, SCM utilization remains suboptimal because ofsubstantial technical hurdles.

Limestone has been interground with cement clinker to makePortland-limestone cement. Limestone is softer and more easily groundthan cement clinker and forms predominantly in the ultrafine fraction.Because limestone has no cementitious or pozzolanic properties, onlylimited quantities of limestone can be interground with cement withoutseriously affecting strength, durability and other performance criteria.Until recently, ASTM C-150 did not permit any limestone addition toTypes I-V cement. In 2003, Hawkins et al. of the Portland CementAssociation published a paper entitled “The Use of Limestone in PortlandCement: A State-of-the-Art Review”, which advocated a change in ASTMC-150 to permit up to 5% limestone addition in OPC. In 2004, ASTM C-150was amended to permit limestone additions of up to 5% in Types I-Vcement. In 2012, ASTM approved a proposal to amend ASTM C-595 (blendedcements) to permit inclusion of 5-15% limestone. These standardsindicate that the use of limestone as a substitute for cement clinker islimited compared to SCMs such as GGBFS and fly ash, which are commonlyused in amounts greater than 15% and which can contribute to long-termstrength development (although they commonly reduce early strength).Because interground Portland-limestone cement must be ground more finelyto avoid serious strength loss, there is little or no economic benefitcompared to OPC. The main benefit appears to be to cement companies,which have an abundant supply of limestone and can use it as a filler tostretch clinker and increase production capacity. Little or no costbenefit is passed on to customers even though such cement is typicallyof lower quality. Blended cements typically can cost the same or morethan OPC, making them less attractive than OPC because of performanceloss. For example, intergrinding clinker, natural pozzolan, andlimestone in Mexico yields blend cements with pour performance. From atechnical standpoint, a major drawback is the inability to control therespective particle size distributions (PSDs) of the cement andlimestone particles when interground. This creates variability anduncertainty in performance.

Researchers have used separately processed very fine or ultrafinelimestone (sometimes called “nano-limestone”) to replace cement clinker,including to augment strength in high volume fly ash (HVFA) mortars.Ultrafine limestone has also been used in ultra-high performanceconcrete (UHPC) as an ultrafine mineral filler similar to silica fume todecrease pore size and increase paste density. In ultrafine limestone,most or all of the particles are less than about 8 μm in size). Thoughfound to enhance strength, ultrafine limestone is typically as expensiveor more expensive than OPC and is therefore not economically feasiblefor general purpose cements and concrete.

A promising source of low cost limestone or other mineral fines isleftover quarry fines (sometimes called “rock dust” or “quarryby-products”) from aggregate manufacture. Aggregates are typicallylimestone or igneous rock of volcanic origin. By way of background,processing of crushed stone for use as construction aggregate consistsof blasting, primary and secondary crushing, washing, screening, andstockpiling operations. Quarry by-products are produced during crushingand washing operations. According to a publication by the FederalHighway Association (FHWA-RD-97-1480) (last modified Mar. 8, 2016),there are generally three types of quarry by-products resulting fromthese operations: screenings, pond fines, and baghouse fines.

“Screenings” refers to the finer fraction of crushed stone thataccumulates after primary and secondary crushing and separation on a4.75 mm (No. 4) sieve. The size distribution, particle shape, and otherphysical properties can be somewhat different from one quarry locationto another, depending on the geological source of the rock quarried, thecrushing equipment used, and the method used for coarse aggregateseparation. Screenings contain freshly fractured faces, have a fairlyuniform gradation, and do not usually contain large quantities ofplastic fines. Screenings are a uniformly sized, fine, sandy materialwith some silt particles. Screenings commonly range in particle sizefrom 3.2 mm (⅛ inch) down to finer than 75 μm (No. 200 sieve). Normally,the percentage of particle sizes finer than 75 μm is 10% or less byweight. Stockpiles of screenings may contain some particles up to 4.75mm (No. 4 sieve) ( 3/16 inch) in size, which is usually the screen sizeused for separation of fine and coarse aggregates. Some weathered rockor overburden material may be present in the screenings from certainprocessing operations

“Settling pond fines” refers to the fines obtained from washing crushedstone aggregate. During production, the coarser size range (greater thanNo. 30 sieve, or 0.60 mm) from washing may be recovered by means of asand screw classifier. The remainder of the fines in the overflow isdischarged to a series of sequential settling ponds or basins, wherethey settle by gravity, sometimes with the help of flocculatingpolymers. “Pond clay” is usually used to describe waste fines derivedfrom the washing of natural sands and gravels. Pond fines, wheninitially recovered from the pond, consist of low solids content,fine-grained slurry, usually with 90-95% of the particles finer than 150μm (No. 100 sieve) and 80% or more finer than 75 μm (No. 200 sieve).

“Baghouse fines” are produced in quarries that operate as dry plantsbecause of dry climatic conditions or a lack of market for washedaggregate products. Dry plant operation requires the use of dustcollection systems, such as cyclones and baghouses, to capture dustsgenerated during crushing operations. These dusts are referred to asbaghouse fines. Although particle sizing may vary somewhat with finesfrom different types of stone, the range in particle size is from 75 μm(No. 200 sieve) down to 1 μm or finer. Baghouse fines can be a source of“nano-limestone” when milled or classified to average particle size ofabout 1-8 μm.

It is estimated that in the U.S. alone at least 159 million metric tons(175 million tons) of quarry by-products are generated each year, mostlyfrom crushed stone production operations. As much as 3.6 billion metrictons (4 billion tons) of quarry by-products may have accumulated in theU.S. According to FHWA-RD-97-1480, it is assumed that very little of the159 million metric tons (175 million tons) produced annually are used,especially pond fines. In a recent survey, three states (Arizona,Illinois, and Missouri) indicated that quarry by-products have been usedas an embankment material, and three other states (Florida, Georgia, andVermont) indicated some use of quarry by-products in base or subbaseapplications. Use has been made of limestone screenings as agriculturallimestone, and baghouse fines from quarry sources have been used asmineral filler in asphalt paving. Limited quantities of baghouse fineshave been provided and/or milled and/or classified to providenano-limestone for laboratory testing; however, there has been noconsistent use of these or other quarry fines in concrete.

Quarry fines can be used in coal mines as “mine safety dust”.Combustible coal dust that is emitted into the air and settles onobjects in a coal mine creates a dangerous risk of mine explosions. Coaldust also causes “black lung” in miners. Dusting of coal mines with minesafety dust reduces the danger of explosions by diluting the combustibledust in the mine with a noncombustible dust, sometimes by misting withwater to wash particulates out of the air. The fineness desired forsafety mine dust is 100% passing a No. 20 sieve (0.85 mm) and at least50% passing a No. 200 sieve (0.075 mm). Because silica-based dust isharmful if inhaled, limestone-based quarry fines (or rock dust) areconsidered to be a safer option for mine safety dust because they havelow silica content. An example of limestone-based mine safety dust isproduced and sold as Coal Mine Rock Dust by Staker Parson, headquarteredin Ogden, Utah (“Staker”), a division of Oldcastle and CRH. Staker ownsand operates an aggregate quarry that produces limestone and dolomiticlimestone aggregates for many of Staker's ready-mix concrete facilitiesin Utah. Leftover quarry fines are collected, further milled, and soldto coal mine operators. Similar products are manufactured by othercompanies, such as Graymont, Blue Mountain Minerals, E. Dillon &Company, Carmeuse, and Omya. Quarry fines are not commonly used byconcrete companies in the manufacture of concrete notwithstanding thismaterial is made by concrete companies or aggregate producers, arereadily available in the same locations as aggregates used in concrete,are a low cost by-product (e.g., retailing at about $2 to $8 per ton inbulk), and are produced in great abundance.

The reported reason that the cement and concrete industries have triedbut failed to effectively use quarry fines in concrete is that theynegatively and unpredictably increase water demand and negatively andunpredictably affect rheology (flow and workability properties).Jeknavorian et al., of W. R. Grace, published a paper in 2010 entitled“Use of Chemical Admixtures to Modify the Rheological Behavior ofCementitious Systems Containing Manufactured Aggregates,” 2010 ConcreteSustainability Conference, National Ready Mixed Concrete Association(“Grace Article”). The Grace Article detailed the negative andunpredictable effects of quarry fines on rheology and other propertiesof concrete and noted that the most effective way to offset the negativeeffects of using manufactured sand containing large amounts of quarryfines is by increasing cement and/or SCM content. The Grace Article alsostated that the main reason for using quarry fines is to producesustainable concrete with locally produced materials notwithstanding thenegative effects of quarry fines on concrete. However, using more cementmakes concrete less sustainable. The Grace Article also explored theundesired interaction between polycarboxylate-based superplasticizersand clay-bearing aggregates containing high quantities of quarry fines.To address this issue, the Grace Article evaluated the interaction ofboth natural and manufactured sands with a bio-polymer typeviscosity-modifying agent (VMA), a class of admixture used withangular-shaped fine aggregates. An admixture company attempting to findan admixture for quarry fines reportedly abandoned the project due tofailure or lack of interest from the concrete industry.

Another reason why quarry fines are difficult to use is they do not fitwithin any specified category of materials used in concrete. The onlytwo options explored by concrete companies and researchers has been totreat quarry fines either as an SCM, used to replace or augment OPC, oras an aggregate. Because quarry fines do not behave like typical SCMsand are even finer than fine aggregates, their effect on strength andrheology is unpredictable and usually negative. The following questionwas asked at an academic cement conference in November 2017: “What islimestone powder? Cementitious binder or aggregate?” An expert replied:“Neither.” To which the follow-on question was asked: “What ASTMstandard specifies how limestone powder is to be used in concrete?” Theexpert replied: “There isn't one.” This blind spot in ASTM standards,common practice, and among experts in the field highlights why it hasheretofore been difficult, if not impossible, to intelligently utilizequarry fines and/or limestone powder to manufacture concrete havingpredictable strength and rheology.

Other mineral materials discarded in vast quantities include bottom ashfrom coal combustion, metallurgical slags (e.g., steel slag produced byscrap reprocessing), stone dust (e.g., marble dust) from stone cuttingoperations, mine tailings, discarded shale from oil shale extraction,discarded sand from tar sands extraction, washout fines from concreteand/or mortar manufacture (wet or dried), and ground recycled concrete.Such materials are often similar in minerology to aggregates used inconcrete, are therefore also “quarry fines” or “mineral fines” and arerarely if ever used as aggregates or fillers.

Attempts have also been made to utilize concrete washout fines inconcrete. Concrete washout fines are formed by washing out a concretetruck or other concrete mixer with water to remove unused fresh concreteas a slurry and removing coarse aggregate particles, such as rock andpea gravel. Washout fines typically include Portland cement, such ashydrated Portland cement, partially hydrated Portland cement, and/orunhydrated Portland cement, fine aggregate particles, water, andoptionally supplementary cementitious materials and/or chemicaladmixtures. Washout fines can be dewatered and placed in piles fordisposal and/or used as road base or fill material. Both wet and driedwashout fines typically have high alkalinity and can have a pH of 10 orhigher. The effects on water demand and set time are highlyunpredictable such that widespread use of concrete washout fines has notbeen technically feasible

The inability of the concrete industry to effectively utilize quarryfines and other waste mineral fines is not surprising since anythingthat creates unpredictability, increased water demand, and/orperformance loss is rejected by the concrete industry, which requirespredictable and reproducible results when producing concrete guaranteedto satisfy prescribed standards set by building codes and engineers.Accordingly, there exists a long-felt but unsatisfied need to find a wayto beneficially utilize quarry fines and other waste mineral fines inconcrete, with predictable strength and rheology, in order to producemore sustainable concrete. The failure of cement, concrete, andadmixture companies to develop a systematic, reliable, and easilyfollowed approach to utilize quarry fines, other waste mineral fines, orlimestone powder in concrete, notwithstanding their great abundance, lowcost, and the tremendous efforts the past two decades to make moresustainable concrete, highlights the problem, the lack of any viablesolution to the problem, and the acuteness of the long-felt butunsatisfied need.

SUMMARY

Disclosed herein are compositions and methods for manufacturingcementitious compositions that contain quarry fines, limestone powder,mine tailings, ground recycled concrete, concrete washout fines (wet ordried), and/or other waste minerals (collectively “mineral fines”) withpredictable water demand, predictable rheology, predictable strength,predictable admixture requirements, and other performance benefits. Anexample method comprises mixing together hydraulic cement, mineralfines, an aggregate fraction, and water so that the cementitiouscomposition has a “defined water-to-cementitious binder ratio” (“definedw/cm”) (or “design w/cm”), and wherein a first portion of the mineralfines is defined and apportioned as forming part of the cementitiousbinder so as to contribute to the defined w/cm and a second portion ofthe mineral fines is defined and apportioned as forming part of theaggregate fraction so as to not contribute to the defined w/cm.Replacing both a portion of cementitious binder and aggregate withmineral fines can significantly reduce both clinker content and costwhile maintaining desired and predictable strength, water demand,rheology, durability, admixture requirement, and other performanceproperties.

An example cementitious composition comprises hydraulic cement, mineralfines (e.g., having a D90 between about 30 μm and about 500 μm, about 40μm and about 300 μm, or about 50 μm and about 150 μm), an aggregatefraction, and water so that the cementitious composition has a definedw/cm, and wherein a first portion of the mineral fines is defined andapportioned as forming to part of the cementitious binder so as tocontribute to the defined w/cm and a second portion of the mineral finesis defined and apportioned as forming part of the aggregate fraction soas to not contribute to the defined w/cm. Attributing a portion of themineral fines as “cementitious binder” can reduce clinker content andaccount for the effect of the mineral fines on water demand withoutsubstantially overstating or understating it. Attributing a portion ofthe mineral fines to the aggregate fraction (e.g., as an “ultrafineaggregate”, some or all of which is dispersed within the cement paste)provides a strength-enhancing filler effect by increasing total powderin the cement paste without substantially overstating or understatingits effect on strength. The mineral fines can beneficially increaseparticle packing density of the cement binder particles and yield adenser cement paste. They can also reduce autogenous, plastic, anddrying shrinkages.

To bridge the size gap between cementitious binder and fine aggregate(sand), the mineral fines are substantially finer than the fineaggregate, with a D90 as defined herein, and coarser than thecementitious binder, which also follows from the D90 defined herein. TheBlaine fineness of the mineral fines is advantageously less than about375 m²/kg, or less than about 350 m²/kg, or less than about 325 m²/kg,or less than about 300 m²/kg, or less than about 275 m²/kg, or less thanabout 250 m²/kg, or less than about 225 m²/kg, or less than about 200m²/kg, or less than about 175 m²/kg, or less than about 150 m²/kg, orless than about 125 m²/kg, or less than about 100 m²/kg, or less thanabout 75 m²/kg, or less than about 50 m²/kg, or less than about 25m²/kg. The minimum Blaine fineness can be at least about 15 m²/kg, or atleast about 25 m²/kg, or at least about 35 m²/kg, or at least about 50m²/kg.

There is test data suggesting that cement paste made with mineral finescan bind more strongly to coarse aggregates, leading to the hypothesisthat proper use of mineral fines can densify cement paste in theinterfacial transition zone (ITZ) between the bulk paste and coarseaggregate surfaces where paste strength is usually at a minimum due to agradient of increasing w/cm in the direction from the bulk paste towardthe coarse aggregate surface. It is further hypothesized that cementparticles shrink when hydrating, causing higher plastic shrinkage ofpaste in the ITZ, which can form micro-fissures that can decreasepaste-aggregate bond strength and/or create pores that provide a pathwayfor ion transport, which can negatively affect durability and increasethe chance of chemical attack of the cement paste and/or alkali-silicareaction (ASR) at the aggregate surface. Mineral fines are non-shrinkingand are believed to provide nucleation sites for cement crystal growth.Both of these effects may substantially increase paste density andreduce paste shrinkage in the ITZ, yielding higher paste-aggregate bondstrength and/or improved resistance to chemical attack.

In some embodiments, it can be advantageous to identify a cutoffparticle size between fine and coarse mineral fines particles, which canbe used to define the particles as either “cement” (or “cementitiousbinder”) or “aggregate” (or “non-cementitious filler”) depending onwhether they are smaller or larger than the cutoff particle size. By wayof example and not limitation, if the cutoff particle size were definedas 45 μm, mineral fines at or smaller than 45 μm can be apportioned ordesignated as “cement” or “cementitious binder” that contribute to (areaccounted for in) the defined w/cm, and particles larger than 45 μm canbe apportioned or designated as “aggregate” that does not contribute to(and is not accounted for in) the defined w/cm, for purposes ofdesigning concrete or other cementitious compositions having predictablewater demand, rheology, and/or strength. The cutoff particle size can beempirically determined or it may be arbitrarily set or approximatedbased on experience. In general, the cutoff particle size can be anyreasonable value that works in accordance with the disclosed methods.For example, it can be between about 15 μm and about 75 μm, or betweenabout 20 μm and about 65 μm, or between about 25 μm and about 55 μm, orbetween about 30 μm and about 50 μm.

Defining or attributing a portion of mineral fines as “cementitiousbinder” that contribute to the “defined w/cm” during design andmanufacture of concrete can perhaps be understood as fictitious orarbitrary because they are not ordinarily considered to be “cementitiousbinders.” The term “defined w/cm” as used herein for purposes ofdesigning and manufacturing concrete (which can also be called a “designw/cm”) can be different than the “actual w/cm” (or simply “w/cm” inordinary parlance) as defined by ASTM, AASHTO, EN, engineers, concretecompanies, or other established standards. Using conventional designmethods or definitions, the actual w/cm (or w/cm) will usually excludemineral fines as not being a cementitious binder, or they may considerall of the mineral fines as “cementitious binder.” As such, the definedw/cm used to design concrete having predictable strength and rheologywill typically lie between a “higher actual w/cm” when none of themineral fines are counted as forming part of the cementitious binder anda “lower actual w/cm” when all of the mineral fines are counted asforming part of the cementitious binder. Though perhaps fictitious orarbitrary, it has now been discovered that using a defined w/cm (ordesign w/cm) by defining one portion of mineral fines as “cementitiousbinder” and another portion as “aggregate” is much more accurate andpredictive of the rheology and strength of the concrete. When none ofthe mineral fines are defined as cementitious binder, but no adjustmentis made to account for water that is absorbed into the mineral fines(e.g., to make a saturated surface dry (SSD) aggregate), a higher actualw/cm is assumed, which underestimates both water demand and strength.Conversely, when all of the mineral fines are defined as cementitiousbinder, even though mineral fines do not typically react with water, alower actual w/cm is assumed, which overestimates both water demand andstrength. Using a design w/cm through proper apportionment of mineralfines between cementitious binder and aggregate is a powerful new toolbecause it more accurately and reproducibly predicts actual water demandand strength of the concrete mix. This, in turn, reduces orsubstantially eliminates uncertainty and lack of reproducibility, whichare typically encountered when assuming either a higher or lower w/cmthan the defined w/cm (or design w/cm) as used herein.

The hydraulic cement binder may comprise ordinary Portland cement (OPC)as defined by ASTM C-150 or blended cement under ASTM 595 or ASTM 1157.Blended cement can be made by intergrinding and/or separate processingand blending. Ordinary Portland cement (OPC) and blended cementstypically have a D90 between about 35 μm and about 45 μm. Alternatively,the cement binder may comprises a narrow PSD cement having a lower D90and/or higher D10 compared to OPC, which reduces the amount of coarseparticles not able to fully hydrate and/or the amount of ultrafineparticles that increase water demand without providing a correspondingstrength benefit. The cement binder can also include calciumsulfoaluminate (CSA) cement, supersulfated cements, oil well cements,geopolymer cements, and other hydraulic cements known in the art.

Supplementary cementitious materials (SCMs) having pozzolanic and/orcementitious activity can be used and beneficially provide a substantialportion of fine and/or ultrafine particles of the overall cementitiousbinder system. Substituting at least a portion of the ultrafine cementparticles (e.g., below about 3 μm) with ultrafine SCM particlessubstantially reduces water demand because ultrafine SCM particles donot significantly react with and consume water in the early stagesduring mixing and placement of concrete. SCMs are also less likely toflocculate like ultrafine cement particles during early stages of mixingand placement. Ultrafine SCMs are much more pozzolanically reactive thanless fine SCM particles, greatly enhancing their strength contributionto the cementitious binder system. Mineral fines can provide asubstantial portion of coarse particles in the cement paste. A coarseSCM may be included to provide particles that are coarser than thecement particles. In a well-optimized cementitious binder system, asubstantial portion (e.g., ≥30%, ≥40%, ≥50%, or majority) of theultrafine particles less than 3 μm may comprise SCM particles, asubstantial portion (e.g., majority) of medium sized particles between3-30 μm may comprise hydraulic cement particles, and a substantialportion (e.g., ≥30%, ≥40%, ≥50%, or majority) of coarse particlesbetween 30-150 μm may comprise mineral fines, optionally in combinationwith coarse SCM particles between 30-150 μm. Strength and durability canbe increased by increasing the overall powder content in the cementpaste through the use of mineral fines that provide a substantialportion (e.g., ≥30%, ≥40%, ≥50%, or majority) of particles between30-150 μm. It will be appreciated that mineral fines are not required tohave particles as large as 150 μm or be devoid of particles larger than150 μm.

It has also been found that using a relatively small quantity ofsupplemental lime (e.g., 0.2-4.8% of hydrated lime by weight ofcementitious binder) can improve rheology and enhance both early andlate age strengths. It is believed that supplemental lime acceleratesand is consumed in the pozzolanic reaction when a pozzolanic SCM isused. Hydrated lime adds calcium ions to the system while only addinghydroxyl ions. This feature helps restore proper ion balance in theevent that the SCM consumes excessive calcium ions required for properhydration of hydraulic cement. It also raises the pH of the system andmay increase the rate of the pozzolanic reaction. It has been found thata relatively small quantity of supplemental lime usually works betterthan a large quantity. Using more supplemental lime than can be consumedin the pozzolanic reaction decreases strength by forming weak voids orpockets of soft filler particles. The ability of supplemental lime toreact pozzolanically is limited by its low water solubility such theproper amount of supplemental lime is more closely related to the amountof water in the system than the stoichiometric amount that mighttheoretically react with the pozzolan.

It has also been found that using a relatively small quantity ofsupplemental sulfate (e.g., 0.2-2.5% of plaster of Paris by weight ofthe cementitious binder) to help maintain proper sulfate balance canhelp maintain normal set time, which can extend workability, and enhanceearly and late age strengths. A sulfate deficiency may occur when asubstantial quantity of sulfate-carrying OPC is reduced and replacedwith SCMs containing aluminates, which can compete for sulfate providedby the OPC. The tendency of mineral fines to accelerate cement hydrationmay also cause sulfate deficiency. The use of superplasticizers andother admixtures to deflocculate fine cement particles can increase thesurface area of cement particles exposed to water, which can causesulfate deficiency. Where a large amount of cement is replaced withother materials so that the water-to-cement ratio (w/c) is substantiallyhigher than the water-to-cementitious binder ratio (w/cm), the excesswater bathing the cement particles can increase cement hydration andcause sulfate deficiency.

In another aspect of the disclosed technology, a cementitiouscomposition comprises ground Portland cement clinker and sulfate tocontrol setting, a supplementary cementitious material (SCM) havingpozzolanic properties, mineral fines comprising particles less than 50μm in size, and at least one accelerator selected from the groupconsisting of lime, quicklime, hydrated lime, and Type S lime and thatis included in an amount in a range of 0.1% to 4.8% by combined weightof hydraulic cement, SCM, and mineral fines having a particle size lessthan 60 μm, or less than 50 μm. Such composition may or may not includemineral fines having a particle size greater than 50 μm, or greater than60 μm. Such composition may optionally include supplemental sulfate(e.g., 0.2-2.5% of plaster of Paris by weight of the cementitiousbinder).

Mineral fines can be blended with one or more performance-enhancingadditives to yield a performance-enhancing particulate pre-mix that canbe added to concrete or other cementitious mixture to substitute for aportion of the cement and/or aggregate components normally used inaccordance with a given mix design. Performance-enhancing additives mayinclude one or more of supplemental lime, supplemental sulfate,alkanolamines, water-reducing admixtures, superplasticizers,accelerators, retardants, and the like. Because mineral fines arenon-reactive, additives containing water (e.g., calcium sulfate slurryor paste scrubber biproducts) can be blended with mineral fines withoutpremature hydration, as would occur if added to a hydraulic cementbinder prior to being used to make a fresh cementitious mixture.

The performance-enhancing particulate premix can be used to replace aportion of cementitious binder, including OPC, but especially blendedcements comprising OPC and at least one SCM selected from slag, fly ash,bottom ash, natural pozzolan, ground glass, metakaolin, silica fume, andthe like. Because of its low cost, which is less than, similar to, oronly marginally more than the cost of aggregate, the premix may also beused to replace a portion of sand or other aggregate. Because waterdemand of the performance-enhancing particulate premix is typically lessthan cement, but more than aggregate, using it to replace both a portionof the cementitious binder and aggregate portions strikes an optimalbalance that enhances performance without significantly increasing, andin some cases reducing, water demand. Mineral fines reduce bleeding andsegregation, thereby reducing the need for expensive viscosity modifyingagents (VMAs) in the case of high strength concrete that includessubstantial quantities of superplasticizers. Reducing or eliminatingVMAs can yield high strength concrete that is less sticky and lessthixotropic.

Concrete washout fines, whether wet or dried, typically have highalkalinity and may include a substantial quantity of free lime. In suchcases, it may be desirable to passivate and neutralize possibledetrimental effects of high alkaline values by blending carbon dioxidewith concrete washout fines before or during mixing of concrete. Atleast some of the added carbon dioxide can beneficially react with freelime and form nano-sized mineral particles (e.g., calcium carbonate) insitu within the fresh concrete or other cementitious mix (e.g., having aD90 less than 0.5 μm). Nano-sized mineral particles can be formed insitu using any known process. An economical way to form nano-sizedmineral particles in situ is by introducing carbon dioxide (CO₂) gasinto a fresh cementitious mix, which reacts with calcium ions to formnano-sized calcium carbonate (CaCO₃) particles. The CO₂ can also reactin situ with other metal ions to form other nano-sized mineralparticles, such as magnesium carbonate (MgCO₃) particles. The nano-sizedmineral particles are typically smaller than even the smallestcementitious binder particles and therefore fill interstitial spacesbetween the cement particles. This increases the particle packingdensity of particles in the cementitious paste. The nano-sized mineralparticles can also provide nucleation sites that promote formation ofcementitious binder crystals, such as calcium silicate hydrates, calciumaluminate hydrates, other aluminosilicate hydrates, and the like.Formation of nano-sized mineral particles can densify cement paste andincrease concrete strength.

These and other advantages and features of the invention will becomemore fully apparent from the following description and appended claims,or may be learned by the practice of the invention as set forthhereinafter.

BRIEF DESCRIPTION OF THE DRAWINGS

To further clarify the above and other advantages and features of thepresent invention, a more particular description of the invention willbe rendered by reference to specific embodiments thereof, which areillustrated in the appended drawings. It is appreciated that thesedrawings depict only illustrated embodiments of the invention and aretherefore not to be considered limiting of its scope. The invention willbe described and explained with additional specificity and detailthrough the use of the accompanying drawings in which:

FIG. 1 is a flow chart illustrating an example method for manufacturinga cementitious composition containing mineral fines;

FIG. 2 is a flow chart illustrating an example method for apportioningmineral fines between cementitious binder and aggregate;

FIG. 3 is a flow chart illustrating another example method forapportioning mineral fines between cementitious binder and aggregate;

FIG. 4 is an example particle size distribution (PSD) chart thatschematically illustrates the PSD of mineral fines and how finer andcoarser mineral fines particles can be apportioned between cementitiousbinder and aggregate for designing and/or manufacturing cementitiouscompositions;

FIG. 5 is a box diagram that schematically illustrates quantities ofmineral fines apportioned between cementitious binder and aggregate;

FIGS. 6A-6E are PSD charts illustrating different mineral fines and howfiner and coarser mineral fines particles can be apportioned betweencementitious binder and aggregate for designing and/or manufacturingcementitious compositions;

FIG. 7 is a flow chart illustrating an example method of designing acementitious composition containing mineral fines;

FIG. 8 is a flow chart illustrating an example method of manufacturing acementitious composition containing mineral fines;

FIG. 9 is a flow chart illustrating an example method of designing andmanufacturing a performance-enhancing particulate pre-mix containingmineral fines and performance-enhancing additive; and

FIG. 10 is a flow chart illustrating an example method of manufacturinga cementitious composition with reduced clinker content using aperformance-enhancing particulate pre-mix.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS I. Introduction

Disclosed herein are compositions and methods for effectively usingquarry fines, limestone powder, mine tailings, ground recycled concrete,concrete washout fines (wet or dried), and/or other waste minerals(collectively “mineral fines”) in concrete with predictable performance,such as predictable water demand, rheology, and admixture requirement,similar or higher strength and durability, and reduced shrinkage. Thecompositions and methods disclosed herein can be used to reduce clinkercontent in concrete. They can enhance effectiveness of SCMs used toreplace a portion of Portland cement clinker.

In some embodiments, a method of designing and manufacturing concrete tobeneficially utilize mineral fines involves selecting materials havingboth fine and coarse particles and apportioning them betweencementitious binder and aggregate. For example, it can be beneficial todefine and apportion a first portion of mineral fines as “cementitiousbinder” for purposes of designing and manufacturing concrete having adefined water-to-cementitious binder ratio (defined w/cm) and define andapportion a second portion of mineral fines as “aggregate” (e.g.,“ultrafine aggregate”) that does not factor into the defined w/cm.

In some embodiments, a concrete composition includes mineral finesapportioned between cementitious binder and aggregate. A first portionof mineral fines is defined and apportioned as “cementitious binder” forpurposes of defining the w/cm of the concrete, and a second portion ofmineral fines is defined and apportioned as “aggregate” (e.g.,“ultrafine aggregate”) that does not factor into the defined w/cm.Surprisingly and unexpectedly, when a first portion of mineral fines isapportioned or defined as forming part of the “cementitious binder” soas to contribute or factor in to the defined w/cm and a second portionis apportioned or defined as forming part of the “aggregate” so as tonot contribute or factor in to the defined w/cm, concrete can bedesigned and manufactured with predictable properties, includingpredictable water demand, rheology, strength, and other performancecriteria.

Without being bound to theory, and by way of example and not limitation,it has been found that mineral fines having a D90 in a range of about 50μm to about 150 μm and a D10 in a range of about 1 μm to about 30 μm,and which contain particles that are both larger and smaller than thelargest cement particles found in OPC (e.g., which are typically betweenabout 35-50 μm), include a first fraction of particles that can bedefined as forming part of the cementitious binder and a second fractionof particles that can be defined as forming part of the aggregatefraction. To be certain, mineral fines, such as coarse limestone,dolomitic limestone, granite powder, stone dust, marble dust, minesafety rock dust, mine tailings, and at least coarse particles in shaleflue dust, are generally non-cementitious and non-pozzolanic and are notactually a “cementitious binder”. They absorb but do not chemicallyconsume water, are essentially a non-reactive filler, and generally havelower water demand compared to similarly sized cement particles.Nevertheless, mineral fines have a surface area with particle surfacesthat must be wetted and therefore “consume” some amount of water byabsorption and adsorption. In general, mineral fines consume or absorbless water than cement but more water than sand or other fine aggregate.Designing and manufacturing concrete so that a first portion of mineralfines is defined and apportioned as forming part of the cementitiousbinder that contributes or factors into the defined w/cm and a secondportion is defined and apportioned as forming part of the aggregate thatdoes not contribute or factor into the defined w/cm, facilitatesreliable and predictable design and manufacture of concrete havingdesired rheology, strength, admixture requirements, and otherperformance criteria.

By way of illustration, one can envision that the portion of mineralfines smaller than a specified particle size (e.g., below 20 μm, 25 μm,30 μm, 35 μm, 40 μm, or 45 μm) are “cement” or “cementitious binder” andthat the portion of particles above the specified particle size are“aggregate.” In practice, this distinction may be arbitrary but is agood way to envision how or why mineral fines can be apportioned betweencementitious binder and aggregate when designing and manufacturingconcrete and other cementitious compositions. It may also be useful indetermining what percentage of mineral fines is defined as “cementitiousbinder” and what percentage is defined as “aggregate.” In addition,while mineral fines that are coarser than cement particles are hardly“ultrafine” from the standpoint of cement particle size, they can bethought of as providing or comprising an “ultrafine aggregate” whencompared to larger particles in typical fine aggregate (or sand) inconcrete or mortar.

In practical terms, concrete designed and manufactured using theforegoing criteria of apportioning or defining mineral fines betweencementitious binder and aggregate can have both reduced clinker contentand reduced fine aggregate content. The mineral fines can in essencestraddle the line between the cementitious binder and fine aggregatefractions, replacing a portion of each. Because mineral fines usuallycost substantially less than OPC, they reduce cost by reducing clinkercontent. Even if mineral fines are more expensive than fine aggregate,as long as the cost of mineral fines is less than the combined cost ofthe hydraulic cement and aggregate they replace, the net result isreduced cost, all other things being equal.

Moreover, the design and manufacture of concrete using mineral fines inthe foregoing manner permits further reductions in clinker content whenused together with one or more supplementary cementitious materials(SCMs) having pozzolanic properties. SCMs such as fly ash, GGBFS, andnatural pozzolans are slow reacting and typically reduce early strengthand/or retard setting. On the other hand, at least some mineral fines(e.g., containing limestone and/or dolomitic limestone) can act as anaccelerator to offset early strength reduction and/or set retardationwhen using SCMs. Because SCMs and mineral fines typically have lowerwater demand than OPC, overall apportioned cementitious binder contentcan be increased and/or the defined w/cm reduced, both of which increaseconcrete strength and durability. In addition, when mineral fines areapportioned between cementitious binder and aggregate, the effectivewater-to-powder ratio (w/p) is lower than both the defined w/cm andactual w/cm, which can further increase strength due to the “fillereffect.” The w/p will usually be lower than the w/cm of a conventionalcementitious composition used as a reference or starting point whendesigning a new cementitious composition. In summary, the defined w/cmarrived at by, or used when, apportioning mineral fines between“cementitious binder” and “aggregate” has been found to be a powerfulnew tool for designing and manufacturing concrete having predictablerheology, admixture requirements, and strength.

All four of the water-to-cement ratio (w/c), defined or design w/cm,actual w/cm, and w/p can be useful when designing and manufacturingconcrete having a desired strength (e.g., compressive strength) andrheology (e.g., slump). The w/c is useful in understanding andpredicting the nature and extent of hydration of Portland cement. Thedesign w/cm, actual w/cm, and w/p are useful in understanding andpredicting the combined strength and rheological attributes provided bythe Portland cement, SCM, and mineral fines fractions.

The foregoing design and manufacturing criteria were initiallydiscovered when designing concrete and mortar using limestone powder(e.g., having a D90 in a range of about 50 μm to about 200 μm and a D10in a range of about 1 to about 30 μm). It was determined that limestonepowder (e.g., Marble White 80 of Specialty Minerals), which is used as afine white aggregate in precast concrete and glass fiber reinforcedconcrete (GFRC), can be apportioned between the cementitious binder andaggregate portions when designing precast concrete and GFRC havingreduced clinker content. In example embodiments, the amount of Portlandcement (e.g., white cement) was reduced by about 50-60%, with a portionof the “removed” white cement being “replaced” with a white-coloredGGBFS and another portion being “replaced” by simply increasing theamount of Marble White 80 previously used only as “aggregate.” In suchmixes, a portion of limestone powder was deemed “cement” for purposes ofdefining the cementitious binder content and another portion was deemed“aggregate” to arrive at proper volume. The resulting compositions hadsimilar or higher strength than commercial compositions made using onlywhite cement as cementitious binder. Examples of cementitiouscompositions made using a ternary blend of white cement, white-coloredGGBFS, and limestone powder are disclosed in U.S. Pat. No. 9,957,196,the disclosure of which is incorporated herein in its entirety.

In particle size optimized compositions, the cement, SCM, and mineralfines fractions can have complementary PSDs that yield a cementitiousbinder system having a broadened PSD compared to the individualparticulate components. The mineral fines are generally coarser than andhave a particle size distribution (PSD) that complements rather thanentirely matches and overlaps the PSD of the hydraulic cement. Using afine or ultrafine SCM that is finer than hydraulic cement can alsocomplement rather than match the PSD of the hydraulic cement. An exampleis fine fly ash (FFA) or ultrafine fly ash (UFFA) formed by grinding orclassifying fly ash to remove or comminute coarse particles so as tohave a D90 of less than about 25 μm, 20 μm, 17.5 μm, 15 μm, 12.5 μm, 10μm, or 8 μm. Another example is silica fume. Another example is fineGGBFS having a D90 of less than about 30 μm, 25 μm, 22.5 μm, or 20 μm.Another is ultrafine natural pozzolan (e.g., ultrafine pumice, volcanicash, calcined shale, or metakaolin formed by ultragrinding) having a D90of less than about 25 μm, 20 μm, 17.5 μm, 15 μm, 12.5 μm, 10 μm, or 8μm. Together, fine or ultrafine SCM, medium size hydraulic cement (e.g.,OPC or narrow PSD cement), and relatively “coarse” mineral fines havinga D90 between about 30 μm, 40 μm, or 50 μm to about 80 μm, 100 μm, 150μm, 200 μm, or 300 μm, yield a ternary blend with an overall PSD that issubstantially broader than the respective PSDs of the individualcomponents. This approach reduces water demand, increases particlepacking density of cementitious and SCM particles, increases pastedensity, increases SCM reactivity, and permits mineral fines to providea powerful filler effect. In this way, mineral fines can increasestrength due to the filler effect without providing too many fine orultrafine particles (as occurs when using ultrafine or nano-limestone)that would otherwise compete with the cement and SCM particles whenfilling the fine and ultrafine regions of the overall PSD of the powder(cementitious binder plus mineral fines).

Fine SCMs are highly reactive and can impart substantially higher earlyand/or late strength compared to SCMs of normal PSD. Fine and ultrafineSCMs typically begin reacting after the cement fraction initially setsto form a rigid or semi-rigid structure. Nonetheless, during initialmixing and placement, fine SCMs, even ultrafine fly ash (UFFA), are atleast temporarily “unreactive,” do not consume water other than bysurface wetting, and therefore can greatly reduce water demand. Usingless water to achieve the same rheology can substantially increase bothshort and long-term strengths. Therefore, using a fine or ultrafine SCMin place of at least some of the fine or ultrafine cement particles cansubstantially improve flow and strength. It may also be beneficial insome cases to include a coarse SCM, such as dedusted fly ash having aD90 in a range of about 75 μm to about 125 μm and a D10 in a range ofabout 10 μm to about 30 μm, to augment the coarse particles provided bymineral fines. The coarse SCM can provide additional strength byadditional filler effect, later age pozzolanic reactions, and/or denserpaste.

It was also determined that replacing a portion of hydraulic cement withmineral fines and one or more SCMs having pozzolanic properties canalter the balance of calcium, silicate, aluminate, and sulfate ions inthe mixture, which can have a moderate to profound effect on thehydration mechanism. Substantially altering the ion balance in theaqueous solution during initial mixing and/or in the pore solution aftersetting, can create problems, such as reduced early strength, reducedlate-age strength, and loss of workability. It was determined that suchproblems can be addressed and at least partially offset by adding minorquantities of one or more common and relatively inexpensive additives.

For example, it was discovered that adding a relatively small amount oflime, such as quicklime or hydrated lime (e.g., Type S lime used inmortar), can significantly increase early and late age strengths.Without being bound to theory, it is hypothesized that using SCMs havingpozzolanic activity consumes calcium ions pozzolanically and lowers thepH to below what is required for proper setting, early strengthdevelopment, and/or late age strength development. Adding a small butsignificant amount of quicklime or hydrated lime, which is only slightlysoluble in water, up to and somewhat exceeding the amount required toform a saturated calcium hydroxide solution, may increase the pH andrestore proper calcium ion concentration during early hydration andsetting and also provide calcium ions and higher pH to increase laterpozzolanic reactions. However, using too much lime can be detrimentalbecause amounts that cannot ultimately dissolve or otherwise be consumedin the pozzolanic reaction may decrease mortar strength (e.g., becausehydrated lime particles that form part of the cement paste are very softand can act as a weak filler). Quicklime, if not fully hydrated to formhydrated lime in situ before final set, can be deleteriously expansive.It may be preferable to use hydrated lime, which is already hydrated andtherefore not expansive, when it is desired to add more lime than whatcan readily dissolve. Nevertheless, quicklime can be desirable due toits higher solubility than hydrated lime if added in amounts that canquickly dissolve or otherwise be consumed during early stages of mixing,setting, and hardening.

In addition, the use of SCMs having pozzolanic activity and mineralfines may negatively affect sulfate balance, leading to loss ofworkability, set retardation, delayed strength development, and lowerultimate strength. For example, when SCMs and mineral fines replacePortland cement, the quantity of sulfate carried by the Portland cementis reduced by the same percentage as the percent reduction in Portlandcement. However, the increased w/c resulting when maintaining the sameor even lower w/cm can change how Portland cement hydrates and alterproper sulfate balance. In theory, a higher w/c may mean fasterconsumption of sulfate and hydration of the aluminate and aluminoferriteminerals in cement clinker. For example, it was observed by researchersat Calmetrix, Inc. that using a superplasticizer to deflocculate cementparticles exposes more of the cement particle surfaces to hydration,resulting in faster consumption of sulfate and higher sulfaterequirement. A similar phenomenon may occur when the w/c is increased byreplacing OPC with SCMs and mineral fines, which do not react with andconsume significant water apart from adsorption during initial mixing.That means more water is available to wet the cement particles and agreater surface area of the cement grains may be exposed to water,resulting in faster consumption of sulfate and higher sulfaterequirement.

Another cause of sulfate deficiency is the presence of aluminates inSCMs such as fly ash, GGBFS, and natural pozzolans, which can consumesulfate ions required for proper hydration of Portland cement. This canresult in loss of workability, set retardation, delayed strengthdevelopment, and long-term strength reduction. Some mineral fines mayalso include aluminates that can cause sulfate deficiency. Whilelimestone may theoretically partially offset the effects of insufficientsulfate through formation of calcium carboaluminates, this reaction andits interplay with ettringite formation and later depletion ofettringite (AFt) to form monosulfoaluminates (AFm) are not wellunderstood. It may be safer to assume that limestone powder cannotcompletely offset negative effects of insufficient sulfate, particularlybecause limestone powder has very low solubility, while uncontrolledhydration of aluminates can occur in minutes. Limestone powder mayprovide positive effects later on, but during early stages of hydrationand set control it is better to ensure there is sufficient sulfate tocontrol hydration of aluminates in the cement and SCM fractions. Inaddition, there is some evidence that added sulfate helps SCMs to morequickly and completely react pozzolanically over time, which increasesultimate strength.

Whether or not there is a sulfate deficiency can be determined usingcalorimetry, such as calorimeters provided or operated by Calmetrix, andmeasuring heat release as a function of time when a cement blend issubjected to hydration conditions. A properly sulfate-balanced cementbinder system will usually have a signature heat release curve. Toolittle sulfate results in insufficient formation of ettringite and/orpremature depletion of ettringite to monosulfate, which permitaluminates to hydrate uncontrollably with water to form calciumaluminate hydrates. Rapid formation of calcium aluminate hydrates causesloss of workability and delayed setting (e.g., by coating tricalciumsilicate crystals and inhibiting their proper hydration). It has beenfound that adding supplemental sulfate, such as plaster of Paris,gypsum, anhydrite, or alkali metal sulfate, can improve rheology, avoidloss of workability, reduce or eliminate delayed setting, and providehigher early and ultimate strengths. As with supplemental lime, theamount of supplemental plaster of Paris, gypsum, or anhydrite should notsubstantially exceed the ability of it or its hydration products todissolve and be consumed by aluminates since calcium sulfate dihydratehas low solubility and will act as a weak filler if it remains unreactedwithin cement paste over time. In addition, unhydrated plaster of Paristhat persists after setting can cause delayed ettringite formation andlong-term expansion. In summary, use of the disclosed design criteriafor using mineral fines, coupled with use of one or more SCMs, sometimeswith addition of supplemental lime and/or sulfate, has yielded mortarand concrete of acceptable or superior strength at greatly reducedclinker content. In some cases, mortar and concrete with low clinkercontent have the same or higher strength compared to control mixes madewith high clinker content.

In the case where wet or dried concrete washout fines are used as partor all of the mineral fines, they can be passivated by mixing with CO₂either before or during manufacture of freshly mixed concrete. Due tothe formation of nano-sized mineral particles in situ (e.g. CaCO₃ and/orMgCO₃), the resulting composition may include at least two differentsize categories of mineral particles that can complement the particlesize distribution of the hydraulic cement binder: (1) nano-sized mineralparticles formed in situ within the fresh cementitious mix (e.g., havinga D90 less than 0.5 μm) and (2) macro-sized mineral fines of larger size(e.g., having a D90 of 50-300 μm) processed separately from thecementitious binder. The result is a ternary blend ofcomplementary-sized particles that synergistically interact to form acementitious paste of high strength per unit weight of cementitiousbinder. If a fine or ultrafine SCM is used, a quaternary blend is formedcomprising in situ formed nano-sized mineral particles, fine orultrafine SCM, hydraulic cement, and mineral fines.

II. Definitions

Information regarding hydraulic cement, supplementary cementitiousmaterials (SCMs), binary, ternary, and quaternary cement-SCM blends, andcementitious compositions that can be made using such materials aredisclosed in U.S. Pat. Nos. 7,799,128, 7,972,432, 8,323,399, 8,377,201,8,414,700, 8,551,245, 8,845,940, 8,974,593, 9,067,824, 9,102,567,9,108,883, 9,376,345, 9,388,072, 9,492,945, 9,738,562, 9,758,437,9,790,131, 9,957,196, 10,131,575, 10,246,379, and 10,350,787, thedisclosures of which are incorporated herein in their entirety.

The term “Dx”, where x is a numeric value between 0 and 100 and Dx is adesignated particle size, means the percentage of particles in adistribution of particles that is at or below the designated particlesize. For example, a particulate material with a “D90” of 75 μm meansthat 90% of the particles are 75 μm or smaller (i.e., are 90% passing at75 μm, or No. 200 sieve) and 10% of the particles are larger than 75 μm.Similarly, a particulate material with a D10 of 20 μm means that 10% ofthe particles are 20 μm or smaller (i.e., are 90% passing at 20 μm) and90% of the particles are larger than 20 μm. A particulate material witha D50 of 45 μm means that 50% of the particles are 45 μm or smaller(i.e., are 50% passing at 45 μm) and 50% of the particles are largerthan 45 μm.

The terms “water-to-cement ratio” and “w/c refer to the ratio of waterto hydraulic cement (e.g., Portland cement) and is typically expressedas a weight ratio. For example, a cementitious composition comprising300 pounds of water and 400 pounds of hydraulic cement would have awater-to-cement ratio (w/c) of 0.75. The term “w/c” as used hereintypically disregards and does not consider supplementary cementitiousmaterials (SCMs) and mineral fines. The w/c does consider sulfate addedto control setting of hydraulic cement and may also consider the amountof additives, such as supplemental lime and supplemental sulfate, thatprovide calcium and sulfate ions and which augment the calcium andsulfate ions provided by the hydraulic cement.

The terms “water-to-cementitious binder ratio” and “w/cm” are typicallyunderstood to refer to the ratio of water to total cementitious binder,including hydraulic cement and supplementary cementitious material(s)(SCM), but excluding unreactive mineral fines, and is typicallyexpressed as a weight ratio. For example, a cementitious compositioncomprising 300 pounds of water and 600 pounds of combined hydrauliccement and SCM(s) would have an actual water-to-cementitious binderratio (w/cm) of 0.5. The “actual w/cm” as used herein is generallysynonymous with the common meaning of the term “w/cm” as used by ASTM,AASHTO, EN, engineers, concrete companies, or other establishedstandards.

The terms “defined water-to-cementitious binder ratio,” “defined w/cm”and “design w/cm” differ from the w/c and (actual) w/cm because theformer also include or account for mineral fines defined or apportionedas “cementitious binder” in addition to the hydraulic cement and SCM(s).The defined w/cm is typically expressed as a weight ratio. For example,a cementitious composition comprising 300 pounds of water and 600 poundsof combined hydraulic cement, SCM, and apportioned mineral fines wouldhave a defined w/cm (or design w/cm) of 0.5. The defined w/cm typicallydisregards and does not consider the portion of mineral fines defined orapportioned as “aggregate”, which can be thought of as simply anon-reactive filler or ultrafine aggregate within or that augments thecement paste.

The terms “water-to-powder ratio” and “w/p” refer to the ratio of waterto total cementitious binder and powder, including hydraulic cement,supplementary cementitious materials (SCMs), and some or the entirety ofmineral fines. The “w/p” is typically expressed as a weight ratio. Forexample, a cementitious composition comprising 300 pounds of water and750 pounds of combined hydraulic cement, SCM, and total mineral finesthat are not true aggregate has a water-to-powder ratio (w/p) of 0.4.The w/p as used is different than the defined w/cm because it alsoaccounts for the portion of mineral fines apportioned to the aggregate.The “cement factor” relates to the amount of cementitious binder and/orcement paste relative to the amount of aggregate. In general and withinlimits, increasing the cement factor typically increases strength at agiven w/cm. An increased cement factor can reduce the tendency of thecementitious composition to experience bleeding or segregation,improving workability, cohesiveness, finishability, and overallperformance. However, it can also increase the propensity for plasticshrinkage, drying shrinkage, and/or autogenous shrinkage. One skilled inthe art can select an appropriate cement factor in combination with theactual w/cm, defined w/cm and/or w/p to yield concrete having desiredperformance attributes.

The terms “hydraulic cement” and “cement” include Portland cement,cements defined by ASTM C150 (Types I-V), blended cements defined byASTM C595 and C1157, and similar materials that contain one or more ofthe four clinker minerals: C₃S (tricalcium silicate), C₂S (dicalciumsilicate), C₃A (tricalcium aluminate), and C₄AF (tetracalciumaluminoferrite). Other examples of hydraulic cement include whitecement, calcium aluminate cement, high-alumina cement, magnesiumsilicate cement, magnesium oxychloride cement, oil well cements (e.g.,Type VI, VII and VIII), magnesite cements, calcium sulfoaluminate (CSA)cement, supersulfated cements, geopolymer cement, and combinations ofthese. Ground granulated blast-furnace slag (GGBFS) and other slags thatinclude one or more clinker minerals may also function as hydrauliccement. They also qualify as SCMs. Some highly reactive class C flyashes have self-cementing properties and can be defined, if desired, toprovide a portion of the “hydraulic cement.”

Consistent with defining GGBFS, slags, and reactive fly ashes as“hydraulic cement,” alkali-activated cements (e.g., alkali-activatedclass C fly ash, alkali-activated GGBFS, and the like) sometimes knownas “geopolymer cements,” are also examples of “hydraulic cements.”Geopolymer cements can benefit from the use of mineral fines as definedherein that are coarser than the particles used to make geopolymercement. In the case of geopolymer cements or other cements that may bedeficient in calcium ions, a source of calcium and/or magnesium ions maybe added to react with the CO₂ to form nano-sized mineral particles.

The terms “supplementary cementitious material” and “SCM” includematerials commonly used in the industry as partial replacements forPortland cement in concrete, mortar, and other cementitious materials,either in blended cements or by self-blending by end users. Examplesinclude moderate to highly reactive materials with both cementitious andpozzolanic properties (e.g., GGBFS, Class C fly ash, and steel slag),moderate to highly reactive pozzolanic materials (e.g., silica fume andactivated metakaolin), and low to moderately reactive pozzolanicmaterials (e.g., Class F fly ash, volcanic ash, natural pozzolans,trass, calcined shale, calcined clay, and ground glass). Through alkaliactivation, it is possible for some SCMs to become hydraulicallyreactive. In a sense, the pozzolanic reaction is a form of alkaliactivation, albeit by less basic and/or lower soluble calcium ions ascompared to more basic and/or higher soluble sodium or potassium ions asin typical geopolymer cements.

The term “mineral fines” refers to waste mineral fines produced duringthe manufacture of crushed rock, such as the manufacture of aggregatesused in concrete. Crushed rock and sand is typically graded using wiremeshes or screens with holes or passages of a specified size. Coarseaggregates are typically separated from finer materials by collectingthe larger rock pieces and particles that are mostly or entirelyretained on a screen having a given mesh size, typically a No. 4 sieve(4.75 mm). Medium aggregates (e.g., pea gravel) and fine aggregates(e.g., sand) are similarly those materials retained on a screen havingan appropriate mesh size. Sand (fine aggregate) that is manufactured bymilling and/or that passes through a No. 4 sieve (4.75 mm) is commonlyscreened using a 100 mesh screen, which retains particles of about 150μm and larger. Particles that fall through the screens are quarry fines.In addition, coarse, medium and fine aggregates can be washed to removefines adhered to the surface. This material is also quarry fines. Insome cases quarry fines are discarded in the state in which they aremade. In other cases they are put through a mill to generate a finerparticulate material (i.e., mine or agricultural rock dust). Forexample, rock dust can be milled to 100 mesh (approximately 150 μm) andsmaller, such as 200 mesh (approximately 75 μm) and smaller. Quarryfines are advantageously sized so as to have a D90 in a range of about50-150 μm, or about 55-125 μm, or about 60-100 μm, or about 70-90 μm.

The term “mineral fines” refers to fines of any mineral, including butnot limited to, waste aggregate particles or fines, waste ormanufactured limestone fines, quarry fines, shale flue dust frommanufacturing lightweight calcined shale aggregates, granite fines,stone dust, rock dust, marble dust, mine tailings, pulverized bottomashes, pulverized metallurgical slags, waste or pulverized shale fromshale oil extraction, and waste or pulverized sand from tar sandextraction, ground recycled concrete, and concrete washout fines (wet ordried). Mineral fines many contain basaltic minerals, other siliceousminerals, and igneous minerals. Virtually any particulate mineralmaterial can used as and/or processed or pulverized to be mineral fines.Unless otherwise specified, the terms “mineral fines” and “quarry fines”are understood to include “limestone powder” (e.g., ground limestonepowder).

In some embodiments, quarry fines are advantageously produced as abyproduct of the production of limestone aggregates and will compriseprimarily limestone (e.g., calcite and/or dolomite). Calcite is amineral having the chemical formula CaCO₃. Dolomite contains a mixtureof CaCO₃ and MgCO₃ and may thought of as having the chemical formulaCaMg(CO₃)₂. Dolomite found in nature does not necessarily have a 1:1ratio of CaCO₃ and MgCO₃. Quarry fines many also contain basaltic andother siliceous minerals but advantageously contains at least 50%, 60%,70%, 80%, 85%, 90%, 95% or 98% calcite and/or dolomite. Some amount ofaluminosilicate clay or mica are permissible so long as they are notunduly expansive and/or do not adversely affect rheology to animpermissible degree.

The term “limestone powder” refers to ground minerals containing mostlycalcite and/or dolomite. Limestone powder is typically manufactured foruse as limestone and will generally be a more pure form of the mineralwith less contaminants than quarry fines or rock dust. Nevertheless,many limestone powders are produced by aggregate manufacturers that alsoproduce quarry fines and may even be quarry fines, albeit a more pureform. Thus, limestone powder, quarry fines, and/or rock dust may besynonymous in some cases. In some cases, limestone powders are made fromwhite limestone powders that have high brightness so that they can beused in decorative precast concrete compositions. In other cases, theycan be off-white or grey. Limestone powders that are particularlyadvantageous for use in the disclosed compositions and methods can havea D90 in a range of about 50-150 μm, or 55-125 μm, or 60-100 μm, or70-90 μm.

Mineral fines may also comprise a wider range of particles and have amore gritty or sandy consistency. In such cases, a smaller proportion ofmineral fines may be defined as “cementitious binder” and largerproportion defined as “aggregate.” Mineral fines of any size range canbe analyzed to determine particle size distribution and apportionedbetween cementitious binder and aggregate using the principles disclosedherein. In general, mineral fines that are coarser and less processedare lower cost and can substitute for a relatively larger portion ofaggregate to further reduce cost of the cementitious composition.Depending on the effect of coarse mineral fines on rheology and/orstrength, the cutoff particle size between “cementitious binder” and“aggregate” can be higher or lower to account for such rheologicaland/or strength differences.

The term “coarse aggregate” generally refers to aggregate particles thatare mostly or entirely retained on a No. 4 sieve, and are generally atleast 4.75 mm ( 3/16 inch) in size, up to about 5 inches, 4 inches, 3inches, 2 inches, 1.5 inch, 1 inch, ¾ inch, or ½ inch. The term “mediumaggregate” generally refers to a subset of coarse aggregate, but ofsmaller average size (e.g., pea gravel, which can include particles ¼ to½ inch in size and/or ⅛ to ¼ inch in size). Coarse aggregates can bemade from any appropriate mineral, such as limestone, granite, basalt,other geological materials, and metallurgical slags. Hence, quarry finesmay include any leftover fines from making coarse aggregate.

The term “fine aggregate” (e.g., sand) generally refers to aggregateparticles that mostly or entirely pass through a No. 4 sieve, and aregenerally less than 4.75 mm ( 3/16 inch) in size and retained on ascreen having an appropriate mesh size. Sand (fine aggregate) can bemanufactured by milling and/or removed from coarse aggregate byscreening. To control consistency, fine aggregate is commonly screenedusing a No. 100 sieve, which retains particles of about 150 μm andlarger, or a No. 140 sieve, which retains particles of about 105 μm andlarger, or a No. 200 sieve, which retains particles of about 75 μm andlarger. Particles that fall through the screen(s) are collected anddiscarded as quarry fines. Fine aggregates can be made from anyappropriate mineral, such as limestone, granite, basalt, othergeological materials, and metallurgical slags. Hence, mineral fines mayinclude any leftover fines from making fine aggregate.

III. Particle Size Distributions

According to one embodiment, the PSD of the hydraulic cement, blendedcement, supplementary cementitious material (SCM), mineral fines, andin-situ formed mineral particles can be defined by their respective D10,D50 and D90, with the D10 approximating the lower PSD endpoint (“LEP”),the D90 approximating the upper PSD endpoint (“UEP”), and the D50approximating the mean particle size (“MPS”) of the PSD. In otherembodiments, the D1, D5, D15, d20 or intermediate value can be used asthe approximate LEP, the D80, D85, D95, D99, or intermediate value asthe approximate UEP, and the D40, D45, D55, D60 or intermediate value asthe approximate MPS.

It can be useful to select cementitious binder materials and mineralfines having complementary rather than completely overlapping PSDs asdefined by their respective D90s, D50s and D10s. This includes, forexample, selecting a hydraulic cement of intermediate fineness, an SCMfiner than the hydraulic cement, and mineral fines coarser than thecement, and optionally a coarse SCM coarser than the cement.

The PSD of a particulate material or blend of particles can bedetermined according to accepted methods for determining particle sizesof ground or otherwise non spherical materials. Particle size can bemeasured using any acceptable method and/or methods yet to be developed.Examples include sieving, optical or electron microscope analysis, laserdiffraction, x-ray diffraction, sedimentation, hydrometer analysis,elutriation, microscope counting, Coulter counter, and Dynamic LightScattering.

A. Hydraulic Cement

A common and useful hydraulic cement that can advantageously be used inthe disclosed compositions and methods is ordinary Portland cement(OPC), as defined by ASTM C-150 and which include Types I-V cement andtheir variants. Types I, II, and V cements typically have a Blainefineness between about 350-450 m²/kg (3500-4500 cm²/g). Type III cementtypically has a Blaine fineness between about 450-600 m²/kg (4500-6000cm²/g). Type 1L, 1P, and C-595 cements can also be used.

Other types of hydraulic cement include aluminate cements,super-sulfated cements, alkali-activated cements, geopolymer cements,and the like.

Alternatively, narrow PSD cements can be used, which have different PSDsthan Types I-V cement. Narrow PSD cements are characterized as having aspread (e.g., UEP−LEP) and endpoint ratio (e.g., UEP/LEP) that are lowerthan the spread and endpoint ratio, respectively, of ordinary Portlandcement (OPC), often substantially lower. Lowering the UEP mayadvantageously reduce the volume of unhydrated cement, which increaseshydration efficiency. Raising the LEP reduces water demand. In oneembodiment, a narrow PSD cement fraction can have a LEP that issubstantially higher, and a UEP that is substantially lower, than therespective LEP and UEP of OPC (e.g., for both Fuller and Tsivilisdistributions).

Nevertheless, OPC can be used in connection with the compositions andmethods disclosed herein and may be a primary source of hydraulic cementto the extent it is readily available and less expensive than narrow PSDcement. However, implementing the present invention using OPC may intime open the door for the use of narrow PSD cements once manufacturersrealize the power and predictability of using carefully selectedparticle sizes for the various cement binder components. The same istrue for fine and ultrafine SCMs, which may become more valuable andwidely used in making ternary blends once the power and simplicity ofthe disclosed methodologies are better understood by cement, concrete,and admixture companies.

The upper endpoint (UEP) of hydraulic cement can be selected to providedesired reactivity and/or fineness in conjunction with or independent ofthe lower endpoint (LEP) and/or a desired particle packing density inconjunction with coarser and mineral fines. The UEP (e.g., D85, D90, D95or D99) can be equal to or less than about 45 μm, 42.5 μm, 40 μm, 37.5μm, 35 μm, 32.5 μm, 30 μm, 27.5 μm, 25 μm, 22.5 μm, 20 μm, 18 μm, 16.5μm, 15 μm, 13.5 μm, 12 μm, or 11 μm. The lower UEP range limit can beabout 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm.

The lower endpoint (LEP) can be selected to provide desired water demandand/or fineness in conjunction with or independent of the upper endpoint(UEP) and/or desired particle packing density in conjunction with one ormore finer SCMs. The LEP (e.g., D1, D5, D10 or D15) can be equal to orgreater than about 0.8 μm, 1.0 μm, 1.25 μm, 1.5 μm, 1.75 μm, 2 μm, 2.5μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, or 8 μm. The upper LEP limit can beabout 6 μm, 8 μm, 10 μm, 12 μm or 15 μm.

The UEP and LEP can also define the spread (UPE−LEP) of the hydrauliccement. For example, and depending on the UEP and LEP of the cement andability or limitations of processing equipment to produce narrow PDScements, the spread can be less than about 40 μm, 35 μm, 30 μm, 25 μm,22.5 μm, 20 μm, 17.5 μm, 15 μm, 13 μm, 11.5 μm, 10 μm, 9 μm, 8 μm, 7 μm,6 μm, 5 μm, or 4 μm.

In some cases, the ratio UEP/LEP can define a narrow PSD cement havingdesired reactivity, fineness and/or particle packing density inconjunction with and mineral fines and one or more SCMs. The UEP/LEP(e.g., D90/D10) of narrow PSD cements can be less than the ratio ofTypes I-V cements as defined by ASTM C-150. According to severalembodiments, the UEP/LEP can be less than or equal to about 30, 27.5,25, 22.5, 20, 17.5, 15, 12.5, 10, 8, 6, 5, 4.5, 4, 3.5, 3, 2.5 or 2.

It will be appreciated that defining the PSD of a narrow PSD cement byratio UEP/LEP is not limited by a particular UEP or LEP or range ofparticle sizes. For example, a first hypothetical narrow PSD cementhaving a D90 of 15 μm and a D10 of 3 μm has a UEP/LEP (i.e., D90/D10) of5 and spread (D90−D10) of 12 μm. By comparison, a second hypotheticalnarrow PSD cement having a D90 of 28 μm and a D10 of 7 μm has a UEP/LEP(i.e., D90/D10) of 4 and a spread (D90−D10) of 21 μm. While the spreadof the second hypothetical narrow PSD cement is greater the UEP/LEP(i.e., D90/D10) is smaller than those of the first hypothetical narrowPSD cement. Thus, the second hypothetical cement has a narrower PSDcompared to the first hypothetical cement as defined by UEP/LEP (i.e.,D90/D10) even though the spread is greater.

B. Mineral Fines

Mineral fines, such as quarry fines, limestone powder, rock dust, safetymine dust, mine tailings, marble dust, stone dust, shale dust, granitefines, ground bottom ash, ground metallurgical slags, waste orpulverized shale from shale oil extraction, waste or pulverized sandfrom tar sand extraction, ground recycled concrete, concrete washoutfines (wet or dried), and other waste or manufactured minerals can beblended with hydraulic cement, such as OPC or narrow PSD cement, toprovide particles that are larger than the coarsest cement particles.Mineral fines can replace some of the cement particles, optionally someof the SCM particles, optionally some of the aggregate, provide a “pasteaggregate” or filler to complement or augment the total quantity ofcementitious binder particles in the cement paste, increase particlepacking density and paste density, provide a filler effect using a lessexpensive component, lower the w/p and/or w/cm, increase fluidity,increase strength, and reduce shrinkage and creep.

When defining mineral fines as “powder” for purposes of determining thew/p, the UEP (e.g., D85, D90, D95 or D99) of the mineral fines can beless than about 500 μm, about 400 μm, about 300 μm, 250 μm, 200 μm, 175μm, 150 μm, 125 μm, 110 μm, 100 μm, 90 μm, 85 μm, 80 μm, 75 μm, 70 μm,65 μm, or 60 μm, with a lower UEP range limit of about 30 μm, 40 μm, 50μm, or 60 μm. In some embodiments, the mineral fines have a D90 in arange of about 50 μm to about 150 μm, preferably about 55 μm to about125 μm, more preferably about 60 μm to about 100 μm, even morepreferably about 70 μm to about 90 μm. Sandier, coarser mineral finescan have particles up to about 5 mm, 4 mm, 3 mm, 2 mm, 1 mm, or 0.5 mm(500 μm). In such cases, the quantity of mineral fines apportioned as“aggregate” will typically be substantially greater than the amountapportioned as “cementitious binder” (as illustrated in FIG. 6C). Largerparticles above about 100 μm, 125 μm, 150 μm, 175 μm, or 200 μm, may notcontribute or factor into the w/p.

The LEP (e.g., D1, D5, D10 or D15) of the mineral fines can be equal toor greater than about 2 μm, 2.5 μm, 5 μm, 7.5 μm, 10 μm, 12.5 μm, 15 μm,17.5 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, or 50 μm, or bewithin a range defined by any two of the foregoing values.

Example mineral fines that can be used in the disclosed compositions andmethods can be obtained from Staker Parson of Ogden, Utah. They aremanufactured at the Keigley quarry located in Genola, Utah, furthermilled to about 200 mesh minus (75 μm and smaller), and sold primarilyas mine safety dust (or Coal Mine Rock Dust) and secondarily as alimestone-based soil amendment by Oldcastle (parent company of StakerParson). A particle size analysis of the Coal Mine Rock Dust wasperformed using a Microtrac-X100 particle size analyzer and determinedto have a very broad, flat PSD curve, with particles as large as about135 μm, a small proportion (3%) smaller than 1 μm, a D90 of about 70 μm,a D50 of about 17 μm, and a D10 of about 2.5 μm. Assuming the particlesize cutoff were 30 μm, which is roughly the d70, one can design andmanufacture a cementitious composition in which about 70% of the rockdust is defined as “cementitious binder” and about 30% as “aggregate,”and that has reasonably predictable rheology (e.g., slump, yield stressand/or viscosity) and strength. Alternatively, assuming the particlesize cutoff were 22 μm, which is roughly the D60, one can design andmanufacture a cementitious composition in which about 60% of the rockdust is defined as “cementitious binder” and about 40% as “aggregate,”and that has reasonably predictable rheology (e.g., slump, yield stressand/or viscosity) and strength.

An example limestone powder that can be used in the disclosedcompositions and methods can be obtained from Specialty Minerals ofLucerne Valley, Calif. It is a ground calcium carbonate sold under thename Marble White 80. It has a D90 of about 150 μm. Marble White 80 caneffectively be apportioned between cementitious binder and aggregate toreduce clinker content when used together with Portland cement (e.g.,white cement) and one or more SCMs (e.g., GGBFS, ground volcanic ash,fly ash, and/or ground pumice). Another example is Blue Mountain FeedFlour, which has a D90 of about 100 μm and a D50 of about 43 μm andwhich is whiter than Coal Mine Rock Dust but less white than Marble 80.

C. Supplementary Cementitious Materials

The PSD of one or more SCM fractions can be defined by the D10, D50 andD90, with the D10 approximating the lower PSD endpoint (LEP), the D90approximating the upper PSD endpoint (UEP), and the D50 approximatingthe mean particle size (“MPS”). In other embodiments, the D1, D5, D15,d20 or intermediate value can be used to approximate LEP, the D80, D85,D95, D99 or intermediate value to approximate UEP, and the D40, D45,D55, D60 or intermediate value to approximate MPS. In some cases, thePSD of a fine SCM fraction may be defined mainly or exclusively in termsof the MPS and/or the UEP, while the PSD of a coarse SCM fraction may bedefined mainly or exclusively in terms of the MPS and/or the LEP.

Blending a fine or ultrafine SCM fraction with OPC or narrow PSD cementcan “replace” at least a portion of fine or ultrafine cement particles,help disperse cement particles, fill fine pore spaces, increasefluidity, increase strength, increase particle packing density, anddecrease permeability. The UEP (e.g., D85, D90, D95 or D99) of a fine orultrafine SCM can be less than about 25 μm, 22.5 μm, 21 μm, 20 μm, 19μm, 17.5 μm, 15 μm, 13 μm, 12 μm, 11 μm 10 μm, 9 μm, 8 μm, 7 μm, 4.5 μm,4 μm, 3.5 μm, or 3 μm or any range defined by two of the foregoingsizes. The lower UEP range limit can be about 1 μm, 2 μm, 3 μm, 4 μm, 6μm, 8 μm, 10 μm, 12 μm, 15 μm, 17 μm, or 19 μm. The LEP (e.g., D1, D5,D10 or D15) can be equal to or greater than about 0.01 μm, 0.03 μm, 0.05μm, 0.075 μm, 0.1 μm, 0.25 μm, 0.5 μm, 0.75 μm, 1.0 μm, 1.25 μm, 1.5 μm,1.75 μm, 2 μm, 2.5 μm, 3 μm, 4 μm, or 5 μm. The upper LEP range limitcan be about 8 μm, 6 μm, 5 μm or 4 μm.

In some embodiments, it may be desirable to include a coarse SCMfraction that is as coarse or coarser than the mineral fines. CoarseSCMs can provide additional filler effect to increase strength, particlepacking density, and paste density, reduce water demand, and providelate age pozzolanic activity. For example, using coarse fly and mineralfines can broaden the PSD of the overall cement blend but offerdifferent benefits. Coarse fly ash can react pozzolanically over timebut may not contribute significantly to early strength. Mineral fines donot react pozzolanically but can provide nucleation sites and/or formcalcium carbonaluminates in order to accelerate early strength gain.Together, coarse fly ash and mineral fines can boost early and latestrengths.

It should also be understood that ordinary SCMs can be used in thecompositions and methods disclosed herein. For example, ordinary fly ashthat has not been classified to form FFA or UFFA, or dedusted to formcoarse fly ash (CFA), can be used to produce concrete of high strengthwhen used in combination with mineral fines having a D90 in a range ofabout 50 μm to about 150 GGBFS having a D90 between about 15-25 μm,17-23 μm, 18-22 μm, or 19-21 μm has been found to be especially usefulwhen combined with Portland cement of lower fineness (e.g., OPC), andmineral fines (e.g., limestone powder) coarser than the Portland cement.

D. In Situ Nano-Sized Mineral Particles

Optional nano-sized mineral particles formed by blending CO₂ withconcrete washout fines and/or in situ within a freshly mixedcementitious composition will typically have a D90 of less than 1 μm,0.9 μm, 0.8 μm, 0.7 μm, 0.6 μm, 0.5 μm, 0.4 μm, 0.3 μm, 0.2 μm, 0.1 μm,0.09 μm, 0.08 μm, 0.07 μm, 0.06 μm, 0.05 μm, 0.04 μm, 0.03 μm, 0.02 μm,or 0.01 μm.

IV. Supplemental Reactants

A. Supplemental Lime

It can be beneficial to add supplemental lime to the cementitiouscompositions. Such lime is “supplemental” to lime released duringhydration of hydraulic cements such as Portland cement. Supplementallime can be added as quicklime (CaO), hydrated lime (Ca(OH)₂) and/orType S lime. Although quicklime is more soluble than hydrated lime, whenexposed to water quicklime is converted into hydrated lime. Therefore,the solubility of hydrated lime, or calcium hydroxide, in water isgenerally a limiting factor for how much supplemental lime can be addedbefore it becomes deleterious. The solubility of calcium hydroxide inwater is reportedly 0.189 g/100 mL at 0° C., 0.173 g/100 mL at 20° C.,and only 0.066 g/100 mL at 100° C. The temperature of concrete whenhydrating is usually above 20° C. and below 100° C. Therefore, thesolubility of hydrated lime is somewhere between 0.173 g/100 mL and0.066 g/100 mL and decreases at increased temperature.

In general, hydrated lime (e.g., Type S lime) is readily available andeasier and safer to handle than quicklime. Hydrated lime also does notconsume water when mixed into a cementitious composition and thereforedoes not affect water demand as much as quicklime. It is also notexpansive like quicklime, which expands when it hydrates. It has beenfound that hydrated lime typically works more predictably thanquicklime, with similar or even superior results from the standpoint ofearly and late strength development.

In some embodiments, the amount of supplemental lime can be below, at,or above the amount required to achieve or maintain saturation in water.The amount of supplemental lime required to maintain a saturated poresolution is dependent on factors such as the amount of free limereleased from the hydraulic cement during hydration, the amount of limeconsumed during cement hydration and pozzolanic reactions, and thesolubility of lime, which decreases with increased temperature.Increased temperature may accelerate consumption of lime, offsettingnegative effects of decreased solubility. Using a more reactive pozzolanmay deplete lime faster than a less reactive pozzolan. The ideal amountof supplemental lime is theoretically that amount that maintains a poresolution saturated with calcium ions over time in conjunction with limereleased from the hydraulic cement and is consumed by pozzolanicreactions. A relatively small excess of supplemental lime can be addedas a reservoir to provide additional lime as it is depleted.

In some embodiments, the amount of supplemental lime is 1-10 times, or1.2-8 times, or 1.5-5 times the amount required to achieve saturation inthe amount of added water. One purpose of adding supplemental lime is tomaintain the pore solution at a pH similar to the pH when using OPCalone. Some SCMs, including fly ash and, in particular, ultrafine flyash (UFFA), can rapidly deplete calcium ions and lower pH of the poresolution, which can interfere with normal cement hydration and/or retardpozzolanic reactions. Adding supplemental lime helps maintain a high pHcharacteristic of normal cement hydration and increase the rate ofpozzolanic reactions. Because lime does not otherwise contribute toconcrete strength but can actually weaken it, it has been found thatusing a relatively small amount of supplemental lime works better thanusing either no added lime or too much added lime. In some embodiments,the amount of supplemental lime based on the total weight ofcementitious binder (cement, SCM and mineral fines apportioned to thecementitious binder) can be about 0.1% to about 10%, or about 0.125% toabout 8%, or about 0.15% to about 6%, or about 0.2% to about 4.8%, orabout 0.3% to about 4%, or about 0.4% to about 3%, or about 0.5% toabout 2.5%, or about 0.6% to about 2%, or about 0.7 to about 1.8% (e.g.,0.8-1.6%).

B. Supplemental Sulfate

When there is insufficient sulfate to properly react with aluminates inthe cementitious binder system, a supplemental sulfate source can beadded, such as calcium sulfate hemihydrate (plaster of Paris), calciumsulfate dihydrate (gypsum), anhydrous calcium sulfate (anhydrite), andalkali metal sulfates (e.g., lithium sulfate). When used, the amount ofsupplemental sulfate based on the total weight of cementitious binder(cement, SCM and mineral fines apportioned to the cementitious binder)can be about 0.1% to about 6%, or about 0.15% to about 5%, or about 0.2%to about 4%, or about 0.3% to about 3%, or about 0.5% to about 2.5%, orabout 0.6% to about 2%, or about 0.8% to about 1.6%.

V. Cementitious Binder Blends and Compositions

Cementitious binder blends designed and manufactured as described hereincan be used in place of OPC, site blends of OPC and SCM, intergroundblends, and other cements and blended cements known in the art. They canbe used to make concrete, ready mix concrete, high performance concrete(HPC), ultrahigh performance concrete (UHPC), self-consolidatingconcrete (SCC) (also known as self-compacting concrete), baggedconcrete, bagged cement, mortar, bagged mortar, grout, bagged grout,molding compositions, bagged molding compositions, or other fresh or drycementitious compositions known in the art. Cementitious binder blendscan be used to manufacture concrete and other cementitious compositionsthat include a hydraulic cement binder, water and aggregate, such asfine and coarse aggregates. Mortar typically includes cement, water,sand, and lime and is sufficiently stiff to support the weight of abrick or concrete block. Oil well cement refers to cementitiouscompositions continuously blended and pumped into a well bore. Grout isused to fill in spaces, such as cracks or crevices in concretestructures, spaces between structural objects, and spaces between tiles.Molding compositions are used to manufacture molded or cast objects,such as pots, troughs, posts, walls, floors, fountains, countertops,sinks, ornamental stone, building facades, and the like.

Water is both a reactant and rheology modifier that permits a freshcementitious composition to flow or be molded into a desiredconfiguration. Hydraulic cement reacts with water, binds the other solidcomponents together, is most responsible for early strength development,and can contribute to later strength development. Blends with highpacking density have reduced void space, which reduces water demand andincreases workability for a given quantity of water.

Cementitious binder blends can be dry-blended or formed in situ whenmaking a fresh cementitious composition containing water and aggregate.Cementitious binder blends include binary, ternary, quaternary, andother blends. In some embodiments, mineral fines and one or more SCMsare blended with hydraulic cement. In some embodiments, cementitiousbinder blends may include one or more chemical additives that affect thechemistry of the aqueous solution, such as accelerating, retarding,and/or water-reducing admixtures, supplemental lime, and supplementalsulfate.

Calcium carbonate in some mineral fines and/or formed in situ using CO₂can enhance strength development. While calcium carbonate hassubstantially lower solubility than lime (only 0.013 g/L at 25°), it canstill contribute some quantity of calcium ions. It can also providenucleation sites for the formation of cement hydration products, mainlycalcium silicate hydrates, calcium sulfoaluminate hydrates, calciumcarboaluminates, and calcium carboaluminoferrites, and the like.

The cementitious binder blend can be mixed with water and one or moreaggregates to form concrete and other cementitious compositions (e.g.,moldable compositions, precast concrete, GFRC, stucco, grout, mortar andthe like). A blend of coarse and fine aggregates of standard size can beused in ready mixed concrete. Other cementitious compositions mayexclude coarse aggregates and only include one or more grades of fineaggregate.

Admixtures known in the industry can be included in cementitiouscompositions. Examples include low-, medium- and/or high-range waterreducers (e.g., lignosulfonates, sulfonated melamine formaldehydecondensate, sulfonated naphthalene formaldehyde condensate,polycarboxylate ethers), superplasticizers (e.g., polycarboxylateethers), set controllers (e.g., sulfates), retardants (e.g.,hydroxycarboxylic acids and carbohydrates), accelerators (e.g., alkaliand alkaline earth metal salts), strength-enhancers (e.g., TEA, TWA,THEED, other amines), corrosion inhibitors (e.g., nitrite salts),hydration stabilizers, and viscosity modifying agents (VMAs) (e.g.,cellulosic ethers).

The water-to-cementitious binder ratio (w/cm) and water-to-powder ratio(w/p) can greatly affect rheology and strength. In general, lowering theamount of water increases strength but negatively affects flow,requiring a superplasticizer and/or water-reducing admixture to maintainproper flow. Thus, there is usually an inverse correlation and tradeoffbetween strength and rheology, all things being equal. Of course, poorrheology can also negatively affect strength if a fresh cementitiouscomposition cannot be properly consolidated or compacted. In addition tow/cm and w/p, the “cement factor” can affect strength. The w/cm can bein any desired value in a range of about 0.2 to about 0.7. Concrete oflow strength typically has a w/cm greater than about 0.55. Concrete ofmoderate strength can have a w/cm between about 0.45 and about 0.55.Concrete of moderately high to high strength can have a w/cm betweenabout 0.33 and about 0.45. Concrete of high to very high strength canhave a w/cm between about 0.22 and about 0.33. Ultrahigh performanceconcrete (UHPC) can have a w/cm between about 0.17 and about 0.25.

The design principals disclosed herein can provide reduced clinkerand/or improved strength through a wide range of water-to-cementitiousbinder ratios and cement factors. Nevertheless, they have been shown toprovide greater improvements in terms of reduced clinker and/or improvedstrength and/or reduced shrinkage at lower w/cm and/or higher cementfactor compared to concrete made using OPC as sole binder or at higherconcentrations relative to SCMs and other mineral additions.

Notwithstanding the principals disclosed herein relative to thebeneficial use of mineral fines, concrete and mortar mixes have beenmade having reduced clinker at improved strength when using ultrafinefly ash (UFFA) and/or coarse calcined shale dust (e.g., flue dust) atmoderate substitution levels and modestly high w/cm (i.e., between about0.35 and about 0.485). This is attributed to the special qualities ofsuch SCMs alone. For example, a UFFA having a D90 of about 8.5 or about10.5 μm was found to provide the same or greater strength whensubstituted for cement in amounts of about 10-30%, or about 15-25%(e.g., 20%), compared to a control mix comprising 100% cement. In somecases, the UFFA was shown to provide a similar strength increase assilica fume at an OPC substitution level of 15% and a w/cm of 0.35. TheUFFA was also shown to provide both greater strength and improvedrheology at an OPC substitution level of 20% and a w/cm of 0.47 comparedto a control mix comprising 100% cement. Calcined shale dust that wascoarser than both OPC and fly ash was shown to provide greater strengthand approximately the same rheology at an OPC substitution level of15-25% (e.g., 20%) and a w/cm of 0.47 compared to a control mixcomprising 100% cement.

VI. Methods of Designing and Manufacturing Cementitious Compositions

Cementitious compositions can be made using any known method, whileincorporating the materials disclosed herein. In some embodiments, acementitious mix is manufactured by blending together a cementitiousbinder, mineral fines, aggregate, and water to form a fresh cementitiousmixture. In some embodiments, CO₂ can be added to the mixture, such asby sparging in CO₂ gas, adding carbonated water, and/or adding crusheddry ice. A fine CO₂ “snow” can be formed by expressing compressed CO₂from a nozzle and mixing the CO₂ snow into the cementitious mixtureusing known means. An example mixing vessel is a central mixer orconcrete mixing truck used to manufacture ready mixed concrete. Concretewashout fines can be passivated by reacting with CO₂, such as before orwhile preparing a cementitious mix.

Reference is made to FIGS. 1-10, which illustrate or relate to exampleembodiments for designing and manufacturing of cementitious compositionsthat utilize mineral fines in an effective and predictable manner toyield concrete and other cementitious compositions having predictablerheology, strength, admixture requirements, and other desirableproperties.

FIG. 1 is a flow diagram illustrating a method 100 for manufacturing acementitious composition containing mineral fines. Step 110 involvescombining hydraulic cement, mineral fines, aggregate and water to form afresh cementitious composition having a defined water-to-cementitiousbinder ratio (defined w/cm). Sub-step or aspect 120 involves a firstpart or portion of the mineral fines being defined as forming part ofthe cementitious binder so as to contribute to or factor into thedefined w/cm. Sub-step or aspect 130 involves a second part or portionof the mineral fines being defined as forming part of the aggregate soas to not contribute to or factor into the defined w/cm.

Method 100 differs from a design or manufacturing method in whichlimestone powder (e.g., nano-limestone) is used as a filler to augmentbut not replace a portion of the cementitious binder, which may comprisePortland cement or a blend of Portland cement and one or more SCMs. Insuch case, there would be no beneficial reduction in cement clinkercontent but merely use of limestone powder as an additive or filler,effectively replacing a portion of the fine aggregate. While usinglimestone powder as an additive can increase the strength of concretedue to the filler effect, it comes at the cost of increased waterdemand, which requires the use of more water, thereby negating orreversing the strength benefit, and/or the use of expensive waterreducing admixtures, which further increases cost. There is noenvironmental benefit from the standpoint of reducing the CO₂ footprintof concrete when clinker content is not reduced. Because fine limestonepowder can cost more than aggregate, replacing less expensive fineaggregate with more expensive limestone powder further increases cost.

Method 100 also differs from a design or manufacturing method in whichlimestone powder (e.g., nano-limestone) is used entirely as a partialsubstitute for Portland cement. In that case, there is a beneficialreduction in cement clinker content but also loss of strength anddurability because the hydraulic cement particles are diluted withunreactive limestone particles. The only way to offset such strengthloss would be to reduce the water to cement ratio (w/c), which reducespaste content, requiring either an increase in aggregate content, pastecontent or both, to maintain proper volume. Increasing aggregate contentgenerally decreases strength and creates a harsher mix (i.e., moregritty and harder to finish). Increasing paste content merely adds backwhat was removed and typically requires several iterations to obtain theproper balance between paste content and w/c to obtain proper strengthand rheology.

The tendency to use limestone powder as either an aggregate or cementsubstitute is based on conventional thinking and the standard practiceof categorizing materials as either “cement” or “aggregate”. A majorU.S. concrete company tried and failed to find a way to effectively uselimestone powder in concrete: when they replaced a portion of thecementitious binder with limestone powder they obtained a beneficialcost reduction but suffered significant strength loss as well; when theyadded limestone powder in addition to the cementitious binder (i.e., asa filler or aggregate that replaced a portion of the fine aggregate)they obtained a beneficial increase in strength but at significantlyincreased cost because the limestone powder cost more than fineaggregate and more water reducing admixture was required. It did notoccur to this company to split the difference and replace part of thecement with a first portion of the limestone powder and replace part ofthe fine aggregate with a second portion of the limestone powder (i.e.,by defining or apportioning a first portion of limestone powder as“cement” or “cementitious binder” and a second portion as “aggregate” or“filler”), which unexpectedly can reduce cost while maintainingcomparable strength, rheology, water demand, and admixture requirements.This inability to think outside the box is consistent with industrypractices.

Simply stated, before the present invention, there was no knownstandard, guideline, or accepted industry practice for characterizingmineral fines as containing both “cementitious binder” and “aggregate”portions when designing and manufacturing concrete and othercementitious compositions. In fact, quarry fines, limestone powder,concrete washout fines, ground recycled concrete, mine tailings, andother mineral fines do not fit any definition of “cement” or standarddefinition of “aggregate” and are in fact neither. An expert in thefield, when asked, stated that mineral fines such as quarry fines and/orlimestone powder are neither cement nor aggregate and confirmed therecurrently is no ASTM standard for using these and other mineral fines inconcrete or blended cement. Nor do most quarry fines and/or limestonepowder fit the definition of a pozzolanic SCM. Therefore, treatingmineral fines as any of “cement”, “SCM,” or “aggregate” is technicallyincorrect. Mineral fines fit no definitions other than “mineraladdition” to cement. As such, the industry has haphazardly attempted touse mineral fines through trial and error testing but with no practicalguidelines. The lack of understanding of how to knowledgeably andeffectively categorize and utilize mineral fines explains why they arerarely if ever used in concrete but continue to pile up unused inenormous quantities.

The present invention seeks to overcome poor practices and confinedthinking by defining or apportioning a first portion of mineral fines as“cement” (or “cementitious binder”) and a second portion as “aggregate”(or “filler”) for the purpose of designing and manufacturing concrete.When this simple, but heretofore unknown, practice is followed, itprovides a simple yet highly effective way to design and manufactureconcrete and other cementitious compositions having predictablerheology, admixture requirements, and strength. The inventive methodsprovide predictable rheology by factoring in a first portion of mineralfines into the determination of the defined w/cm to account for itscontribution to water demand, but without overstating or understatingit. The inventive method provides predictable strength and avoidsoverstating or understanding the effect on water demand by defining andusing a second portion of the mineral fines as an ultrafine “aggregate”to provide a strength-enhancing “filler effect” by effectively reducingthe water-to-powder ratio (w/p) of the cement paste.

Design and manufacturing method 100 is therefore a powerful new tool,technical breakthrough, and methodology that result in new cementitiouscompositions with different ratios of hydraulic cement, mineral fines,aggregate and water, but with predictable results from the standpoint ofrheology, admixture requirements, and strength. It is an entirely newway of treating materials that have heretofore been characterized asbeing one, and only one, of cement, SCM, or aggregate, and which fit noactual definition other than “mineral addition” that can be intergroundwith cement clinker in amounts up to 5% according to ASTM C-150 orbetween 5-15% according to ASTM C-595, or “filler” that can replace aportion of the fine aggregate.

FIG. 2 is a flow diagram illustrating a method 200 for apportioningmineral fines between cementitious binder and aggregate when designingand/or manufacturing a cementitious composition. Step 210 involvesmeasuring and/or obtaining the particle size distribution (PSD) of themineral fines. Step 220 involves identifying a cutoff particle sizebased on the PSD of the mineral fines, optionally based on the effect onwater demand, which cutoff particle size can be used to apportion thematerial. Step 230 involves designating or defining particles smallerthan the cutoff particle size as “cementitious binder” for the purposeof determining or defining the defined water-to-cementitious binderratio (defined w/cm) of the cementitious composition being manufacturedand/or designed. In general, the cutoff particle size can be anyreasonable value that works in accordance with the disclosed methods.For example, it can be between about 15 μm and about 75 μm, or betweenabout 20 μm and about 65 μm, or between about 25 μm and about 55 μm, orbetween about 30 μm and about 50 μm. Step 230 involves designating ordefining particles larger than the cutoff particle size as “aggregate”(or filler) that is not used to determine the defined w/cm of thecementitious composition. The cutoff particle size can be determined bytesting a few different cementitious compositions using a source ofmineral fines having relatively constant PSD and identifying the sizethat yields the best and/or most predictable results of strength, waterdemand, and admixture requirements. By way of example and notlimitation, if the cutoff particle size were determined to be 30 μm andthis is the D40 of the mineral fines, 40% of the particles would be ator smaller than this size and apportioned or defined as “cementitiousbinder” for the purpose of determining the defined w/cm of thecementitious composition, and 60% of the of the particles would belarger than the cutoff size and apportioned or defined as “aggregate”that is not used to determine the defined w/cm (but is included in thew/p). In many or most cases it means the mineral fines replace a bothportion of cementitious binder and a portion of aggregate. This accountsfor the competing effects on both water demand and strength withoutoverstating and/or understating them.

FIG. 3 is a flow diagram illustrating an alternative method 300 forapportioning mineral fines between cementitious binder and aggregatewhen designing and/or manufacturing a cementitious composition. Step 310involves measuring, obtaining and/or estimating the particle sizedistribution (PSD) of the mineral fines. Step 330 involves designatingor defining a first portion of mineral fines as “cementitious binder”for the purpose of determining the defined w/cm of the cementitiouscomposition being manufactured and/or designed. Step 330 involvesdesignating or defining a second portion of mineral fines as “aggregate”that is not used to determine the defined w/cm of the cementitiouscomposition being manufactured and/or designed. The foregoingdesignations or definitions can be somewhat arbitrary. However, it hasbeen found that precision is not normally required as long as asubstantial portion (e.g., 10-85%, 20-80%, 30-70%, 40-60%, 45-55% or50%) of the mineral fines is defined as “cementitious binder” and asubstantial portion (e.g., 15-90%, 20-80%, 30-70%, 40-60%, 45-55% or50%) of the mineral fines is defined as “aggregate.”

In general, finer mineral fines may reasonably be considered to containor approximate more “cementitious binder” particles and fewer“aggregate” particles, and coarser mineral fines may reasonably beconsidered to contain or approximate fewer “cementitious binder”particles and more “aggregate” particles. A few test batches can be usedto determine a reasonable apportionment, mainly by testing rheology,which can be performed in a relatively short period of time, such aswithin 10-30 minutes after initially mixing the test batches. As ageneral rule, apportioning more of the mineral fines as “cementitiousbinder” will improve rheology, while apportioning more of the mineralfines as “aggregate” will improve strength. Striking a desirable balancebetween the two has been found to be remarkably simple compared totraditional trial and error testing, which demonstrates the robustnessof the methodology.

FIG. 4 is a PSD chart 400 that schematically illustrates the particlesize distribution (PSD) of hypothetical mineral fines. PSD chart 400illustrates a first finer portion 410 with particle sizes at or lessthan a defined or approximated particle size cutoff 430 and a secondcoarser portion 420 with particle sizes at or greater than cutoffparticle size cutoff 430. First portion 410 may be considered or definedas “cementitious binder” and second portion 420 may be considered ordefined as “aggregate” for purposes of designing and manufacturingconcrete or other cementitious composition having a defined w/cm anddefined quantity of mineral fines. Chart 400 therefore visuallyillustrates a way to understand the apportioning method 200 shown inFIG. 2 and described above. One can readily see that moving particlesize cutoff 430 to the left reduces the quantity of mineral finesdefined as “cementitious binder” and increases the quantity defined as“aggregate.” Conversely, it may easily be seen that moving particle sizecutoff 430 to the right increases the quantity of mineral fines definedas “cementitious binder” and reduces the quantity defined as“aggregate.” To be sure, mineral fines are in fact neither “cementitiousbinder” nor “aggregate” following known or standard definitions. Theyare merely apportioned or defined this way to facilitate the design andmanufacture of a cementitious composition having predictable rheology,admixture requirements, and strength.

FIG. 5 is a box diagram illustrating how a quantity of mineral fines 500(e.g., having a D90 between about 50-150 μm) can be apportioned betweena cementitious binder portion 510 and an aggregate (or filler) portion520 for purposes of designing and manufacturing a cementitiouscomposition having a defined w/cm and a defined quantity of mineralfines. Box diagram 500 therefore visually illustrates a way tounderstand the apportioning method 300 shown in FIG. 3 and describedabove. One can readily see that apportioning or defining first andsecond portions of mineral fines as either “cementitious binder” 510 or“aggregate” 520 may be somewhat arbitrary based on experience. Again,apportionment need not be viewed as an exacting or rigorous exercisebecause, once again, none of the particles are in fact “cementitiousbinder” or “aggregate” under standard definitions. They are merelyapportioned or defined this way to facilitate the design and manufactureof a cementitious composition having predictable rheology, admixturerequirements, and strength.

FIGS. 6A-6E are PSD charts that illustrate how mineral fines havingdifferent particle size distributions might be apportioned, designatedor defined as “cement” or “aggregate”. FIG. 6A is a PSD chart showing aPSD curve 600 that approximates an average PSD based on three differentPSD measurements for Staker Parson mine rock dust. The rock dust can beapportioned between a first finer portion 605 (which can be treated as“cement” or “cementitious binder”) and second coarser portion 610 (whichcan be treated as “aggregate” or “filler”) based on established orestimated particle size cutoff 615, which is shown as a range ratherthan a discrete particle size. That is because the actual particle sizecutoff may vary depending on the particle sizes of OPC and SCM and/orthe relative amounts of OPC, SCM, and rock dust, and/or the cementfactor, and/or the measured effect of this particular rock dust onrheology and/or strength for given types of concrete (e.g., low, medium,or high strength). The particle size cutoff range 615 is illustrativebecause the actual particle size cutoff may vary within a defined range.

FIG. 6B is a PSD chart showing a PSD curve 620 that approximates a sieveanalysis for a limestone powder from Blue Mountain Minerals identifiedas “Feed Flour.” This material appears to be similar to but somewhatcoarser than the Staker mine rock dust of FIG. 6A, but was found to besuitable for use in the disclosed invention. The Feed Flour can beapportioned between a first finer portion 625 (which can be treated as“cement” or “cementitious binder”) and second coarser portion 630 (whichcan be treated as “aggregate” or “filler”) based on established orestimated particle size cutoff 635, which is shown as a range. Theactual particle size cutoff may vary within a range depending on factorsnoted in the preceding paragraph.

FIG. 6C is a PSD chart showing a PSD curve 640 that approximates a sieveanalysis for limestone-based quarry fines from Blue Mountain Mineralsidentified as “Super Sand.” This material is substantially coarser thanthe rock dust and limestone powder materials of FIGS. 6A-6B, but can besuitable for use in the disclosed invention if properly apportioned.This quarry or mineral fines material can be apportioned between a firstfiner portion 645 (which can be treated as “cement” or “cementitiousbinder”) and second coarser portion 650 (which can be treated as“aggregate” or “filler”) based on established or estimated particle sizecutoff 655, which is shown as a range. The actual particle size cutoffmay vary within a range depending on factors noted in the precedingparagraphs. Because about 75% of the particles in this material arelarger than about 150 μm, and range up to about 4 mm, and about 14% aresmaller than about 75 μm, the quantity of particles treated as “cement”or “cementitious binder” is relatively small compared to particlestreated as “aggregate.” Perhaps about 10-20% of this material may bedefined as “cementitious binder” and about 80-90% defined as“aggregate.” Alternatively, it may be advantageous to supplement thismaterial with a finer material, such as those in FIG. 6A, 6B, 6D or 6Eto boost the “cement” portion.

FIG. 6D is a PSD chart showing a PSD curve 660 that approximates a sieveanalysis for a limestone powder from Specialty Minerals identified as“Marble White 80.” This material appears to be somewhat coarser than therock dust and limestone powder of FIGS. 6A-6B, but was determined to besuitable for use in the disclosed invention. This limestone powder canbe apportioned between a first finer portion 665 (which can be treatedas “cement”) and second coarser portion 660 (which can be treated as“aggregate”) based on established or estimated particle size cutoff 675,which is shown as a range. The actual particle size cutoff may varywithin a range depending on factors noted in the preceding paragraphs.

FIG. 6E is a PSD chart showing an estimated PSD curve 670 for alimestone powder from Blue Mountain Minerals identified as “micro fine”limestone. This material is much finer than any of the materials ofFIGS. 6A-6D but may be suitable as a supplement for any of the materialsof FIGS. 6A-6D to increase the proportion of particles defined as“cement” or “cementitious binder.” If there existed a hypotheticalparticle size cutoff in the location shown by dotted line 685, theentirety of the micro fine material would likely be apportioned entirelyas fine portion 675 and treated as “cement” or “cementitious binder” forpurposes of its expected effect on water demand. While this material mayincrease early strength, it would not be expected to yield higherstrength concrete if used solely to replace a portion of the cement. Itwould be expected to increase strength if used in addition to the cementand to replace part of the aggregate, but would negatively impactrheology and require the use of additional water reducing admixture(s)to offset such effects. From the standpoint of particle packing, only alimited amount of micro fine limestone can be added to the cement(perhaps no more than 10%) before it would decrease particle packing byoverloading the particle system with too many ultrafine particles. Thiswould violate the Fuller principle of broad particle size distribution.

FIG. 7 is a flow diagram that illustrates an example method 700 ofdesigning a cementitious composition containing mineral fines. A firststep 710 involves selecting a cementitious binder content, such aspounds per cubic yard (lb/yd³) (U.S. practice), or kilograms per cubicmeter (kg/m³) (most parts of the world). The selected cementitiousbinder content correlates with the “cement factor” and can be based onknown mix designs and/or standard practices of a concrete manufacturer.To the extent that the new cementitious binder system, including mineralfines, yields a stronger cementitious binder paste, the selectedcementitious binder content can be less than the cementitious bindercontent of a known cementitious mix that is being redesigned accordingto the invention. A second step 720 involves selecting an amount ofhydraulic cement that is less than the selected cementitious bindercontent. For example, if the selected amount of hydraulic cement is 65%of the selected cementitious binder content, it would result in areduction in clinker content of 35% compared to a standard cementitiouscomposition made using hydraulic cement as sole cementitious binder. Athird step 730 involves selecting an amount of SCM to replace all or aportion of the cement reduction. For example, if the cement reductionwere 35%, the selected amount of SCM might be any amount up to orexceeding 35%. However, because the purpose of this method is tosubstitute a portion of the hydraulic cement with mineral fines, theselected amount of SCM can be less than 35%. For example, the selectedamount of SCM might be 25%. That would leave a remaining cementitiousbinder “deficit” of 10% that can be occupied by a powder. A fourth step740 involves selecting an amount of mineral fines to replace anadditional portion of the cement reduction. For example, if the cementreduction were 35%, and 25% of the cementitious binder comprised one ormore SCMs, the amount of mineral fines required to eliminate thecementitious binder deficit would be 10% of the total binder. If othercomponents, such as supplemental lime and/or supplemental sulfate areincluded and considered to form part of the cementitious binder, a lowerquantity of mineral fines may be required to eliminate the cementitiousbinder deficit. A fifth step 750 involves selecting an additional amountof mineral fines so that the total powder content (hydraulic cement,SCM, mineral fines, and optional supplemental lime and/or sulfate)exceeds the selected cementitious binder content. Following thisprocedure permits one to consider the materials selected in steps 720,730 and 740 to contribute to the defined w/cm for purposes of yielding acementitious composition having predictable rheology at a given cementfactor. However, the materials selected in steps 720, 730, 740 and 750will contribute to the overall powder content and affect the strength.An increased powder content also reduces the tendency of thecementitious composition to experience bleeding or segregation,improving workability, cohesiveness, finishability, and overallperformance. Based on the total cementitious paste volume, including allpowders and water, the amount(s) of fine, medium, and/or coarseaggregates can be adjusted to produce concrete of the correct yield(e.g., per cubic yard or cubic meter).

FIG. 8 is a flow diagram that illustrates an example method 800 ofmanufacturing a cementitious composition comprising mineral fines. Afirst step 810 involves selecting a cementitious binder content and awater-to-cementitious binder ratio (w/cm) (i.e., defined w/cm). Thesecan be based on known mix designs and/or standard practices of aconcrete manufacturer in order to design concrete having a desired orpredetermined rheology and strength. A second step 820 involvescombining hydraulic cement, one or more SCMs, a first portion of mineralfines, water and aggregate to form a cementitious composition with theselected binder content and defined w/cm. A third step 830 involvesadding a second portion of mineral fines that is deemed to form part ofthe aggregate, not the cementitious binder, so as to not contribute tothe defined w/cm (but which contributes to the w/p). A fourth step 840involves the optional step of adding one or more of supplemental lime,supplemental sulfate, or other auxiliary components. To be sure, steps820, 830 and 840 need not be performed sequentially or in any particularorder. They can be performed simultaneously and/or partially combinedand/or performed in a different order, including any desired order thatfits within a concrete manufacturer's standard practices. The steps aremerely set forth as separate steps to illustrate how they analyticallyreflect or represent aspects of the new design and manufacturemethodologies disclosed herein.

In some embodiments a method of manufacturing improved or augmentedconcrete incorporating mineral fines, comprises:

A) manufacturing a reference concrete mix of design strength (σ) bycombining:

-   -   (i) a first quantity of cementitious binder (cm) per unit        quantity of concrete;    -   (ii) a first quantity of aggregate (agg) per the unit quantity        of concrete;    -   (iii) a first quantity of water (w) per the unit quantity of        concrete; and    -   (iv) optionally one or more additional components,    -   wherein the reference concrete:        -   (a) has a first water-to-cementitious binder ratio (w/cm);            and        -   (b) yields a hardened concrete with a strength of at least            σ; and

B) manufacturing an augmented concrete mix by combining:

-   -   (i) a second quantity of cementitious binder (cm′) per the unit        quantity of concrete;    -   (ii) a second quantity of aggregate (agg′) per the unit quantity        of concrete;    -   (iii) a second quantity of water (w′) per the unit quantity of        concrete;    -   (iv) a quantity of added mineral fines (mf) per the unit        quantity of concrete; and    -   (v) optionally one or more additional components,    -   wherein the reconfigured concrete mix:        -   (a) has a second water-to-cementitious binder ratio (w/cm′)            greater than w/cm;        -   (b) has a total unit powder quantity (p′) equal to cm′+mf            per the unit quantity of concrete;        -   (c) has a water-to-powder ratio (w/p′) less than w/cm; and        -   (d) yields an augmented hardened concrete with a strength of            at least a.

The “reference concrete mix” is typically a commercial concrete mixproduced and distributed by a concrete manufacturer, but which does notinclude added mineral fines. In the United States, concrete mix designsare typically expressed in amounts of each component per 1 cubic yard(yd³) of concrete. The components of the concrete mix designs expressedin amounts that when combined yield 1 cubic yard of concrete. To make 1cubic yard of concrete, the components of the concrete mix design arecombined in the stated amounts. If more or less concrete is desired, themix design can be infinitely scaled up or down by multiplying thespecified amounts of components in the mix design by the number of cubicyards required or specified. For example, if “x” cubic yards of concreteis/are desired or specified, the manufacturer can simply scale the mixdesign up or down by multiplying each component of the mix design byscaling factor “x” to obtain scaled amounts and combine them to produce“x” cubic yards of concrete. Outside the U.S., concrete mix designs aretypically expressed in amounts of each component per 1 cubic meter (m³)of concrete and can be infinitely scaled up or down as needed bymultiplying each component of the mix design by scaling factor “x” toobtain scaled amounts and combine them to produce “x” cubic meters ofconcrete.

The design and manufacturing methods of the disclosed invention can beapplied to produce an augmented or improved concrete mix designs thatincludes added mineral fines. When this happens, a concrete company thatpreviously produced or currently produces concrete mixes that do notcontain added mineral fines can thereafter produce augmented concretemixes that contain added mineral fines. Because concrete mix designs aretypically specified for specific uses or purposes, the present inventioncan be used to redesign some or all of the concrete company's mixdesigns. In this way, the previously produced concrete mixes are“reference concrete mixes,” and the previous concrete mix designs are“reference concrete mix designs.” The inventiveness of the augmentedconcrete mixes and concrete mix designs can be shown by comparing themto the reference concrete mixes and reference concrete mix designs,respectively, previously made and used by the concrete manufacturer.

The methods disclosed herein can be used to systematically redesign someor all existing concrete mix designs of a concrete manufacturer andthereby replace some or all of the existing concrete mix designs withaugmented concrete mix designs that can be used to produce augmentedconcrete mixes containing added mineral fines. The previous or existingconcrete mix designs are reference concrete mix designs used forspecific purposes, and the augmented concrete mix designs can be used tomake augmented concrete mixes for the same specified purposes as theprevious or existing concrete mixes (which are reference concretemixes). Alternatively, a new concrete manufacturer entering the marketcan use the design methods to create augmented concrete mix designsbased on previously known or existing reference concrete mixes.

In some embodiments, a method of manufacturing augmented concrete by aconcrete manufacturer incorporating mineral fines comprises:

-   -   A) identifying a reference concrete mix design (e.g., of the        concrete manufacturer) for a unit quantity of concrete (e.g.,        yd³ or m³) having:        -   (i) a design strength (σ);        -   (ii) a first quantity of cementitious binder (cm) per the            unit quantity of concrete;        -   (iii) a first quantity of aggregate (agg) per the unit            quantity of concrete;        -   (iv) a first quantity of water (w) per the unit quantity of            concrete;        -   (v) a first water-to-cementitious binder ratio (w/cm); and        -   (vi) optionally one or more additional components;    -   B) the concrete manufacturer preparing or obtaining an augmented        concrete mix design to replace the reference concrete mix        design, the revised concrete mix design having:        -   (i) the design strength (σ);        -   (ii) a second quantity of cementitious binder (cm′) per the            unit quantity of concrete;        -   (iii) a second quantity of aggregate (agg′) per the unit            quantity of concrete;        -   (iv) a second quantity of water (w′) per the unit quantity            of concrete;        -   (v) a second water-to-cementitious binder ratio (w/cm′)            greater than w/cm;        -   (vi) a quantity of added mineral fines (mf) per the unit            quantity of concrete;        -   (vii) a total powder quantity (p′) per the unit quantity of            concrete equal to cm′+mf;        -   (viii) a water-to-powder ratio (w/p′) less than w/cm; and        -   (ix) optionally one or more additional components; and    -   C) the concrete manufacturer manufacturing an augmented concrete        mix according to the augmented concrete mix design.

In some embodiments, the method comprises preparing or obtaining aplurality of augmented concrete mix designs to replace a plurality ofcorresponding reference concrete mix designs and manufacturing aplurality of corresponding augmented concrete mixes according to theplurality of augmented concrete mix designs.

In some embodiments, at least some of the following conditions arepresent:

-   -   cm′<cm;    -   w′<w;    -   total powder in reference concrete mix equals total cementitious        binder (p=cm);    -   p′>cm;    -   agg′<agg;    -   p′<cm;    -   agg′>agg;    -   α=compressive strength;    -   c′<90% c, c′<85% c, c′<80% c, c′<75% c, c′<70% c, c′<65% c,        c′<60% c, c′<55% c, or c′<50% c;

In some embodiments, a method of manufacturing augmented concreteincorporating mineral fines comprises:

preparing an augmented concrete mix by combining:

-   -   ordinary Portland cement (OPC) having a D10 below about 3 μm and        a D90 between about 35 μm and about 45 μm;    -   ground granulated blast furnace slag (GGBFS) having a D90        between about 15 μm and about 25 μm;    -   mineral fines having a D90 in a range of about 50 μm and about        300 μm and a D10 between about 2 μm and about 50 μm;    -   coarse aggregate comprising aggregates retained on a No. 4 sieve        (4.75 mm);    -   fine aggregate comprising aggregates passing a No. 4 sieve        (4.75 mm) and retained on a No. 100 sieve (150 μm); and    -   water; and

allowing or causing the concrete mix to harden.

VII. Performance-Enhancing Particulate Pre-Mix

Mineral fines can be blended with one or more performance-enhancingadditives to yield a performance-enhancing particulate pre-mix that canbe added to concrete or other cementitious mixture to substitute for aportion of the cement and/or aggregate components normally used inaccordance with a given mix design. Performance-enhancing additives mayinclude one or more of supplemental lime (e.g., CaO, Ca(OH)₂, hydratedlime, or Type S Lime), supplemental sulfate (e.g., calcium sulfatehemihydrate, plaster of Paris, calcium sulfate dihydrate, gypsum,anhydrous calcium sulfate, anhydrite, or alkali metal sulfate),alkanolamines (e.g., triethanolamine (TEA) or triisopropanolamine(TIPA)), amines (tetrahydroxylethylethylene diamine (THEED) orpoly(hydroxyalkylated)ethylene diamine) (polyHEED), water-reducingadmixtures, superplasticizers, accelerators, retardants, and the like.Because mineral fines are generally non-reactive, additives containingwater or moisture can be blended with mineral fines without prematurehydration, as would occur if added to a cementitious binder prior tobeing used to make a fresh cementitious mixture. Theperformance-enhancing particulate premix can be made using any knownblending method, including intergrinding, planetary mixers, spraying,and the like.

In some embodiments, the performance-enhancing particulate pre-mixcomprises less than 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 7%, 5%,4%, 3%, 2%, or 1% of hydraulic cement and can be free of hydrauliccement altogether. In some embodiments, the performance-enhancingparticulate pre-mix comprises less than 50%, 45%, 40%, 35%, 30%, 25%,20%, 15%, 10%, 7%, 5%, 4%, 3%, 2%, or 1% of combined hydraulic cementand supplemental cementitious material (SCM) and can be free ofhydraulic cement and SCM altogether. In some embodiments, theperformance-enhancing particulate pre-mix may comprise an intergroundmixture of mineral fines and volcanic ash, pumice, other naturalpozzolan, fly ash, and/or GGBFS.

The performance-enhancing particulate premix can be used to replace aportion of cementitious binder, including OPC, but especially blendedcements comprising OPC and at least one SCM selected from slag, fly ash,natural pozzolan, ground glass, and the like. Because of its low cost,which is less than, the same as, or only marginally more than the costof aggregate, the premix may also be used to replace a portion of sandor other aggregate. Because water demand of the performance-enhancingparticulate premix is typically less than cement, but more thanaggregate, using it to replace both a portion of the cementitious binderand aggregate portions strikes an optimal balance that enhancesperformance without significantly increasing, and in some casesreducing, water demand.

Reference is made to FIGS. 9-10, which illustrate or relate to exampleembodiments for designing and manufacturing a performance-enhancingparticulate pre-mix and cementitious compositions made using thepre-mix, which utilize mineral fines and one or moreperformance-enhancing additives. The methods illustrated in FIGS. 9-10are given by way of example, not limitation, and performance-enhancingparticulate pre-mix compositions can be designed and manufactured usingany desired method.

FIG. 9 is a flow diagram illustrating a method 900 for designing andmanufacturing a performance enhancing pre-mix. Step 910 involvesdetermining a quantity of cementitious binder to be added to a givenquantity of concrete or cementitious composition (e.g., lb/yd³ orkg/m³). Step 920 involves determining a quantity ofperformance-enhancing additive to be added to the concrete orcementitious composition by means of the performance-enhancingparticulate pre-mix. Step 930 involves apportioning mineral finesbetween cementitious binder and aggregate. Step 940 involves determiningan amount of the performance-enhancing additive to be added to themineral fines in order to deliver a proper quantity of theperformance-enhancing additive to the cementitious binder, concrete, orother cementitious composition. Step 950 involves blending thedetermined quantity of performance-enhancing additive with the mineralfines to yield the performance-enhancing particulate pre-mix.

FIG. 10 is a flow diagram illustrating a method 1000 for manufacturing acementitious composition with reduced clinker content. Step 1010involves providing a mix design specifying a predetermined quantity oftotal cementitious binder, total aggregate, water, and optional chemicaladmixture(s), and a defined water-to-cement ratio (defined w/c) and/ordefined water-to-cementitious binder ratio (defined w/cm). A typical mixdesign for concrete specifies the quantity of each material per cubicyard or cubic meter of concrete. Step 1020 involves providing aperformance-enhancing particulate pre-mix as described herein.

Alternatively, some or all of the “pre-mix” can be manufactured in situwhen blending the components of the cementitious composition. Step 1030involves combining the cementitious binder (OPC, optionally with SCM),aggregate, water, and optional chemical admixture(s) to form acementitious composition. Sub-step 1040 involves a first portion of theperformance-enhancing particulate pre-mix contributing to the total (ordefined) cementitious binder content so as to contribute or factor intothe defined w/cm (or defined w/c) and reduce the clinker content of themix design compared to concrete made in the absence of theperformance-enhancing particulate pre-mix. Sub-step 1050 involves asecond portion of the performance-enhancing particulate pre-mixcontributing to the total aggregate content and not the definedcementitious binder content so as to not contribute to the defined w/cm(or defined w/c) and also to reduce sand and/or coarse aggregate contentof the mix design compared to concrete made in the absence of theperformance-enhancing particulate pre-mix. It will be appreciated thatthe performance-enhancing particulate pre-mix may reduce SCM content inaddition to, or instead of, reducing clinker content.

VIII. Attributes of Concrete and Cementitious Compositions

Concrete and other cementitious compositions made according to thedisclosed invention will typically have readily observable attributes orsignatures that set them apart from conventional concrete mix designs,particularly when the disclosed design methods are used to redesign anexisting concrete mix design. For example, a commercial concrete mixdesign will typically have a specified cementitious binder content,specified water-to-cementitious binder ratio (w/cm) (i.e., weight ofwater divided by the combined weight of Portland cement and all SCMs),and specified aggregate(s) content. A new concrete mix design madeaccording to the disclosed invention will typically have one or more ofthe following attributes or signatures:

-   -   (1) higher actual w/c (i.e., weight of water divided by weight        of Portland cement) than the specified w/c of the commercial        mix;    -   (2) higher actual w/cm (i.e., weight of water divided by        combined weight of Portland cement and SCMs, excluding added        mineral fines) than the specified w/cm of the commercial mix        when a portion of cementitious binder is replaced by added        mineral fines that contribute or factor into the defined (or        design) w/cm;    -   (3) lower w/p (i.e., weight of water divided by combined weight        of Portland cement, SCMs, and total added mineral fines) than        the specified w/cm of the commercial mix when a second portion        of added mineral fines does not contribute to and is not        factored into the defined w/cm;    -   (4) a design w/cm that is similar or equal to the specified w/cm        of the commercial mix (within + or −0.03, 0.02, 0.01, or 0.005;    -   (5) total combined Portland cement and SCM (cementitious        binder), excluding added mineral fines, that is less than the        specified cementitious binder content of the commercial mix,        when a portion of the cementitious binder is replaced by added        mineral fines;    -   (6) total powder content, including total combined cementitious        binder and added mineral fines, greater than the specified        cementitious binder content of the commercial mix, when a        portion of the aggregate is replaced by mineral fines;    -   (7) reduced quantity of total (generally fine) aggregate        compared to the commercial mix when replaced by a portion of the        mineral fines;    -   (8) reduced VMA requirement in the case of mix that includes        superplasticizer because a lower w/p and/or more total powder        reduces bleeding and segregation;    -   (9) higher paste density due to increased particle packing        density of total paste particles compared to paste density of        the commercial mix;    -   (10) greater cementitious paste density in the interfacial        transition zone (ITZ) between bulk paste and aggregate surfaces        (e.g., coarse aggregate surfaces) compared to the ITZ in        commercial mix; and    -   (11) greater bond strength between cementitious paste and coarse        aggregates compared to the commercial mix.

IX. Examples

Some examples below utilized mineral fines (i.e., quarry fines)purchased from the Keigley quarry located on Genola, Utah at a pricesubstantially lower than the typical cost of OPC. A ton of the mineralfines was conveniently packaged in forty 50-pound sacks of coal minerock dust stacked on a pallet. In this form, the product was stillsignificantly less expensive than the bulk price of OPC. If purchased inbulk, the cost of mineral fines would be about ⅓ or less than the bulkprice of OPC. This highlights the tremendous cost savings that can berealized by effectively using mineral fines. In the examples below,25-50% of the OPC normally contained in concrete was replaced withvarious SCMs and mineral fines and provided similar or greater strengththan control mixes containing 100% OPC or 80% OPC and 20% fly ash. Afirst particle size analysis of the coal mine rock dust performed usinga Microtrac-X100 particle size analyzer showed a very broad, flat PSDcurve, with particles as large as about 135 μm and a small proportion(3%) smaller than 1 μm, a D90 of about 70 μm, a D50 of about 17 μm, anda D10 of about 2.5 μm. A chemical analysis of the coal mine rock dustshowed that it contained 87% calcite (CaCO₃), 3% dolomite (CaMg(CO₃)₂),3% quartz, 1% K-feldspar, 1% ankerite/Fe dolomite, and 5% illite-mica. Asecond particle size analysis obtained by hydrometer analysis showed apercent passing of 93% at 75 μm, 61% passing at 27 μm, 53% passing at 18μm, 43% passing at 11 μm, 31% passing at 8 μm, 23% passing at 6 μm, 13%passing at 3 μm, and 6.2% passing at 1 μm. A third particle sizeanalysis performed by a Malvern Mastersizer 2000 showed a D90 of about91 μm, a D50 of about 17 μm, and a D10 of about 2.75 μm.

Some examples utilized Feed Flour limestone powder sold by Blue MountainMinerals, Columbia, Calif. It reportedly contains about 90% CaCO₃ andhas a D90 of about 100 μm and a D50 of about 43 μm. It is off-white incolor.

Some examples utilized limestone powder sold by Specialty Minerals inLucerne Valley, Calif. It is a ground calcium carbonate sold under thename Marble White 80. It reportedly has a brightness of 92, specificgravity of 2.7, and contains 98% calcium carbonate, 1.2% magnesiumcarbonate, and less than 0.1% iron oxide. A sieve analysis was performedon a 1000 g sample, with 32.51 g (3.251%) retained on a #70 sieve (212μm), 71.83% (7.183%) retained on a #100 sieve (150 μm), 170.18 g(17.018%) retained on a #140 sieve (106 μm), 246.52 (24.653%) retainedon a #200 sieve (75 μm), and 478.95 g (47.895%) in the pan. The D90 istherefore about 150 μm and the D50 is about 75 μm.

Some examples utilized Class F fly ash produced at the Gaston, Ala.steam power plant and provided by Headwaters, Inc., previouslyheadquartered in South Jordan, Utah, recently acquired by Boral. Variousforms of this fly ash were used, including in its original form (FA) andafter being classified into fine (FFA), ultrafine (UFFA), and coarsefractions (CFA). Classification was performed by RSG, Inc., located inSylacauga, Ala. The PSD of each material was measured by RSG using aMicrotrac-X100 particle size analyzer. The unprocessed fly ash (FA) hada D90 of about 80 μm, a D50 of about 20 μm, and a D10 of about 2.5 μm.The fine fly ash (FFA) after a first classification had a D90 of about20 μm, a D50 of about 7.5 μm, and a D10 of about 1.5 μm. The coarse flyash (CFA) after the first classification had a D90 of about 120 μm, aD50 of about 45 μm, and a D10 of about 20 μm. The FFA was classifiedagain to yield a first ultrafine fly ash (UFFA) having a D90 of about4.6 μm, a D50 of about 2.5 μm, and a D10 of about 1.16 μm, and a secondUFFA having a D90 of about 8.5 μm, a D50 of about 4.6 μm, and a D10 ofabout 1.45 μm. Some examples utilized Class F fly ash produced at FourCorners, Fruitland, N. Mex., power plant, distributed by SRMG, andprovided by Central Concrete, located in San Jose, Calif.

Some examples utilized ultrafine fly ash (UFFA) produced by classifyingfly ash produced at three power plants owned by Pacificorp: Jim Bridger,located in Bridger, Wyo.; Hunter, located in Castle Dale, Utah; andHuntington, located in Huntington, Utah. The fly ashes were classifiedby RSG. The Bridger fly ash was apparently moist and agglomerated andwas not able to be effectively classified or its PSD characterized. TheBridger “UFFA” was therefore the least effective even though it is theonly one of these three fly ashes sold and used commercially in concreteon a consistent basis.

The Hunter and Huntington fly ashes are generally considered to be ofsubstandard quality, are not generally used in concrete, are sometimesused in asphalt, and are typically landfilled (i.e., because ofexcessive carbon and/or a reactivity index below 75). They reportedlyamount to about 750,000 to 1 million tons produced per year. This wouldbe a substantial source of fly ash if it could be beneficiated intousable products of acceptable quality. The Hunter and Huntington flyashes were classified to provide a 20% yield of UFFA product, whichwould amount to about 150,000 to about 200,000 tons per year of highquality UFFA between the two geographically similar situated powerplants.

The PSD of the Hunter UFFA was measured by RSG using a Microtrac X100particle size analyzer and reported to have a D90 of about 7.5 μm, a D50of about 3.1 μm, and a D10 of about 1.1 μm. The PSD was bimodal withpeaks at about 1.3 μm and about 4 μm. The specific gravity of the HunterUFFA was determined to be 2.6375 and the LOI satisfied ASTM C-618. TheHunter UFFA was tested by Wyoming Analytical Laboratories and determinedto contain 44.73% SiO₂, 18.70% Al₂O₃, 13.53% CaO, 2.72% SO₃, 5.78% Fe₂O₃(total SAF=69.21); 5.29% MgO, 1.66% Na₂O, 1.57% K₂O, 0.99% TiO₂, 1.26%P₂O₅, and 3.43% LOI. A calorimetry test indicated some degree of setretardation when used with OPC at 40%.

The PSD of the Huntington UFFA was measured by RSG using a MicrotracX100 particle size analyzer and reported to have a D90 of about 10.5 μm,a D50 of about 3.8 μm and a D10 of about 1.26 μm. The specific gravityof the Huntington UFFA was determined to be 2.534 and the LOI satisfiedASTM C-618 according to NIST analysis. The Huntington UFFA was tested byWyoming Analytical Laboratories and determined to contain 44.94% SiO₂,19.30% Al₂O₃, 4.17% Fe₂O₃ (total SAF=69.11), 9.34% CaO, 2.17% SO₃, 3.35%MgO, 2.87% Na₂O, 1.85% K₂O, 1.07% TiO₂, 0.92 P₂O₅, and 9.02% LOI (makingit non-conforming if accurate). A calorimetry test indicated some degreeof set retardation when used with OPC at 40%.

Some examples utilized coarse calcined shale flue dust produced byUtelite Corporation, Coalville, Utah. The shale flue dust is collectedin the baghouse and is a byproduct produced during the calcining ofshale to make lightweight aggregates. The shale flue dust has notpreviously been used in concrete and, to the best of the knowledge ofUtelite personnel that provided a sample, had never previously beentested in concrete or as a cement substitute. Instead, it isoccasionally used as a filler in asphalt but typically landfilled. ThePSD of the shale flue dust was measured by RSG using a Microtrac X100particle size analyzer and reported to have a D90 of about 114 μm, a D50of about 24 μm and a D10 of about 3.5 μm. The shale flue dust wasdetermined by XRF to contain 56.6% SiO₂, 14.2% Al₂O₃, 6.04% CaO, 2.25%MgO, 4.21% Fe₂O₃, 0.29% Na₂O, 1.98% K₂O, 0.54% TiO₂, 0.21 P₂O₅, 0.72% S,0.02% MnO₂, 0.06% BaO, <0.21% Cr. The chemistry is therefore similar toa Class F fly ash except that shale flue dust has no combustibleelemental carbon.

Some examples used Holcim Type II/V OPC manufactured at Devil's Slidecement plant, Morgan, Utah, and sold at Home Depot, Salt Lake City, Utah(sometimes labeled as Type I/II/V or I/II, previously assumed to be TypeI/II, and now understood to be Type II/V according to generalrequirement for cement in Utah to be Type II/V according to ASTM C-150).Some examples used Lehigh Type II/V cement from Lehigh Hanson cementplant, Cupertino, Calif., and provided by Central Concrete.

Some examples utilized Grade 120 ground granulated blast furnace slag(GGBFS) sold by Lehigh Heidelberg, Stockton, Calif., and provided byCentral Concrete. The GGBFS was determined by XRD to be 97.2% amorphousand by XRF to contain 30.4% SiO₂, 13.7% Al₂O₃, 43.4% CaO, 6.3% MgO, 0.6%Fe₂O₃, 0.1% Na₂O, 0.3% K₂O, 0.6% TiO₂, 4.4% SO₃, and 0.01% MnO₂. The PSDof the GGBFS reportedly has D90 of about 20 μm, a D50 of about 7.5 μmand a D10 of about 1.6 μm.

Some examples utilized a fine clinker ground by Gebr. Pfeiffer atKaiserslautern, Germany, to specifications provided by the inventor. RawType II/V clinker was provided by Drake Cement, located in Paulden,Ariz., and owned by Unacem, Peru. Some examples utilized an intergroundblend of volcanic ash provided by Staker Parson, Ogden, Utah, andlimestone granules provided by Pfeiffer and ground by Pfeiffer tospecifications provided by the inventor. The moisture content of thevolcanic ash as received was 6.0%. Intergrinding the volcanic ash withlimestone reduced the water content of the interground blend to lessthan 0.5%. Strength testing indicates the volcanic ash waspozzolanically activated by intergrinding with the limestone.

Some examples utilized concrete washout fines obtained from Ready MadeConcrete, located in Salt Lake City, Utah. Such fines were removed froma settling pond, placed in a pile to dry, used as road base and fill,and are sold for about $20 a ton in bulk.

Some examples utilized wet concrete washout fines obtained from DeltaIndustries, located in Jackson, Miss. Such fines are typicallyland-filled and have negative value. The wet washout fines were ovendried to remove water before adding to mortar mixes.

Some examples utilized 1-inch aggregate and sand purchased from StakerParson, North Salt Lake, Utah.

Concrete mixes tested herein were prepared using a 3.5 cubic feet rotarymixer and cast into 4×8 inch plastic cylinder molds, allowed to harden,transported to CMT Engineering, Inc., of West Valley City, Utah,demolded, placed into a curing chamber, and tested at designatedintervals (e.g., 3, 7, 28, 91, and 182 days). Mortar mixes were preparedusing a Hobart mixer and cast into 2×2 inch cube molds, allowed toharden, placed into a saturated limewater bath, transported to CMTEngineering, placed into a saturated limewater bath inside the curingchamber, and tested at designated intervals. A lignosulfonate waterreducer and/or superplasticizer was/were employed as needed to maintainadequate rheology (e.g., approximate slump of about 3-6 inches, or7.5-15 cm) and in commercially acceptable amounts.

Comparative Examples 1-5

Comparative Example 1 was prepared from a standard “6-bag” concrete mixcontaining 564 lbs. of OPC per cubic yard and having a design strengthof 5200 psi (35.85 MPa) at 28 days. Comparative Example 2 was preparedfrom a standard 6-bag concrete mix in which 20% of the OPC issubstituted with fly ash. Comparative Example 3 was a further modifiedstandard 6-bag mix in which 30% of the OPC was substituted with fly ashand the sand reduced. Comparative Examples 1-3 are useful control mixesagainst which other concrete mixes can be compared. The compositions ofComparative Examples 1-3 are set forth in Table 1. Comparative Example 4is identical to Comparative Example 2 except that 20% of the OPC wassubstituted with mineral fines instead of fly ash. Comparative Example 5is identical to Comparative Example 3 except that 30% of the OPC wassubstituted with mineral fines instead of fly ash. Comparative Examples4 and 5 do not include an additional quantity of mineral fines deemed asaggregate to replace a portion of the sand.

TABLE 1 Table 1. Mix composition and strength of Control mixes with 100%OPC, 20% and 30% class F fly ash, or 20% and 30% mineral finesComponents (lb/yd³) Comparative Examples Compressive Strength 1 2 3 4 5Holcim II/V OPC 564 451.2 394.8 451.2 394.8 Clinker Reduction (%) 0% 20%30% 20% 30% CO₂ reduction lb/yd³ 0 112.8 169.2 112.8 169.2 Class F FlyAsh 0 112.8 169.2 0 0 Mine Rock Dust 0 0 0 112.8 169.2 Coarse Aggregate1750 1750 1750 1750 1750 Fine Aggregate 1372 1338 1320 1338 1320 Water266.6 266.6 266.6 266.6 266.6 Design w/cm 0.47 0.47 0.47 0.47 0.47Actual w/cm 0.47 0.47 0.47 0.59 0.675 w/c 0.47 0.59 0.675 0.59 0.675 w/p0.47 0.47 0.47 0.47 0.47  3-day (psi/MPa) 3850/26.5 3482/24.0 3050/21.03340/23.0 2980/20.5  7-day (psi/MPa) 4580/31.6 4097/28.2 3870/26.73670/25.3 3360/23.2 28-day (psi/MPa) 5690/39.2 5202/35.9 5010/34.54720/32.5 4000/27.6  3-month (psi/MPa) 6240/43.0 6135/42.3 5910/40.75210/35.9 4910/33.9  6-month (psi/MPa) 6850/47.2 6505/44.9 5960/41.15470/37.7 5190/35.8

Comparative Examples 1-3 show the relative effects of using OPC comparedwith a blend of OPC and fly ash at 20% and 30% substitution. ComparativeExamples 4 and 5 included OPC and mineral fines at 20% and 30%substitution. As expected, the mineral fines, being non-reactive,performed worse than fly ash when used simply as a partial cementsubstitute. But when used in ternary and quaternary blends as describedin working examples below, they permitted substantially higher clinkerreductions at similar to higher strength compared to ComparativeExamples 1-5.

Working Examples—Concrete

The following working examples were designed and manufactured by theinventor and are identified using their mix ID numbers assigned duringtesting. They were manufactured using the concrete mix designs set forthin the tables below. Strength values are also provided.

TABLE 2 Components (lb/yd³) Example (Mix ID) Compressive Strength 10 11A11B 12A 12B Holcim II/V OPC 366.6 394.8 394.8 451.2 366.6 ClinkerReduction (%) 35% 30% 30% 20% 35% CO₂ reduction lb/yd³ 197.4 169.2 169.2112.8 197.4 Class F Fly Ash 84.6 84.6 0 0 0 Huntington UFFA 0 0 0 112.8141.0 Shale Flue Dust 84.6 0 84.6 0 0 Mine Rock Dust 112.8 163.58 163.580 101.5 Type S Lime 22.56 11.28 11.28 0 8.46 Plaster of Paris 5.64 5.645.64 0 2.82 Coarse Aggregate 1750 1650 1650 1750 1705 Fine Aggregate1249 1302 1302 1338 1300 Water 248.2 248.2 248.2 266.6 242.5 Design w/cm0.40 0.43 0.43 0.47 0.39 Actual w/cm 0.44 0.50 0.50 0.47 0.47 w/c 0.680.63 0.63 0.59 0.66 w/p 0.37 0.38 0.38 0.47 0.39  3-day (psi/MPa)2720/18.8 2950/20.3 3250/22.4 3010/20.8 2860/19.7  7-day (psi/MPa)4350/30.0 3800/26.2 3960/27.3 4570/31.5 4490/31.0 28-day (psi/MPa)6160/42.5 4850/33.4 5530/38.1 6480/44.7 6620/45.6  3-month (psi/MPa)7170/49.4 6050/41.7 6620/45.6 7540/52.0 8310/57.3  6-month (psi/MPa)7760/53.5 6060/41.8 7020/48.4 8440/58.2 8920/61.5

Compared to Comparative Examples 1-5, Mix 10 had lower clinker content,higher absolute water-to-cement ratio (w/c), and higher strength at 28,91, and 182 days. Mixes 10, 11A, 11B and 12B all benefited significantlyfrom including mineral fines as both a partial cement replacement and apartial ultrafine aggregate addition. In addition, the inclusion of TypeS lime in each of Mixes 10, 11A, 11B and 12B also appears to haveprovided a strength benefit. The inclusion of plaster of Paris isbelieved to have improved rheology and/or increased strength.

Mix 12A is unique because it included no mineral fines, Type S lime, orplaster of Paris addition but exhibited high strength owing to the useof Huntington UFFA having a D90=10.5 μm, a D50=3.8 μm, and a D10=1.26μm. UFFA was easily dispersed and greatly increased flow compared tousing silica fume.

The foregoing compositions have the following characteristics andprophetic or hypothetical modification range:

Aspect Range Modification Range OPC: 366.6-451.2 lb/yd³ 320-530 lb/yd³Fly Ash/ 0-141 (84.6-141) lb/yd³ 0-180 (60-180) lb/yd³ Pozzolan:Ultrafine 0-112.8 (112.8) lb/yd³ 0-140 (50-150) lb/yd³ Fly Ash: ShaleFlue 0-84.6 lb/yd³ 0-180 (60-180) lb/yd³ Dust: Mineral 0-163.6(84.6-163.6) lb/yd³ 0-200 (50-200) lb/yd³ Fines: Lime: 0-22.56(8.46-22.56) lb/yd³ 0-30 (5-30) lb/yd³ CaSO₄ 0-5.64 (2.82-5.64) lb/yd³0-10 (2-10) lb/yd³ (hemi): Design 0.39-0.47 0.35-0.50 w/cm: Actual0.44-0.50 0.41-0.53 w/cm: w/c: 0.59-0.68 0.55-0.75 w/p: 0.37-0.470.33-0.51

TABLE 3 Components (lb/yd³) Example (Mix ID) Compressive Strength 12C13A 13B 13C 17C Holcim II/V OPC 366.6 451.2 394.8 366.6 423 ClinkerReduction (%) 35% 20% 30% 35% 25% CO₂ reduction lb/yd³ 197.4 112.8 169.2197.4 141 Class F Fly Ash 0 0 0 0 112.8 UFFA 0 0 84.6 141 0 Shale FlueDust 141 112.8 84.6 50.8 0 Mine Rock Dust 101.5 0 56.4 56.4 90.2 Type SLime 8.46 0 0 5.64 5.64 Plaster of Paris 2.82 0 0 0 0 Course Aggregate1705 1750 1685 1687 1700 Fine Aggregate 1304 1338 1300 1300 1260 Water242.5 266.6 248.2 248.2 256.3 Design w/cm 0.43 0.47 0.42 0.42 0.44Actual w/cm 0.47 0.47 0.44 0.44 0.47 w/c 0.66 0.59 0.63 0.68 0.61 w/p0.39 0.47 0.40 0.40 0.41  3-day (psi/MPa) 2960/20.4 4080/28.1 3930/27.13280/22.6 3690/25.4  7-day (psi/MPa) 4420/30.5 4605/31.7 5670/39.15000/34.5 4450/30.7 28-day (psi/MPa) 7390/50.9 6100/42.0 7550/52.17600/52.4 5380/39.1  3-month (psi/MPa) 8580/59.1 7050/48.6 8290/57.28530/58.8 6660/45.9  6-month (psi/MPa) 8980/61.9 7180/49.5 9170/63.29220/63.6 7010/48.3

Mix 13B contained Huntington UFFA, and Mix 13C contained Hunter UFFA.Mixes 12C, 13B, 13C and 17C all appear to have benefited significantlyfrom including mineral fines as both a partial cement replacement and apartial ultrafine aggregate addition. In addition, Mixes 12C, 13C and17C appear to have benefited significantly by including Type S lime.

Mix 13A is unique because it included no mine rock dust, Type S lime, orplaster of Paris addition but exhibited higher strength than any ofComparative Examples 1-5 at all ages owing to the use of calcined shaleflue dust having a D90=114 μm, D50=24 μm and D10=3.5 μm. This materialis an industrial waste product that has not heretofore been used by anyconcrete company to make concrete or other cementitious composition. Itmay be considered to be a form of mineral fines because it is abiproduct of lightweight aggregate manufacture.

The foregoing compositions have the following characteristics andprophetic or hypothetical modification range:

Aspect Range Modification Range OPC: 366.6-451.2 lb/yd³ 320-530 lb/yd³Fly Ash/ 0-112.8 (112.8) lb/yd³ 0-170 (60-170) lb/yd³ Pozzolan:Ultrafine 0-141 (84.6-141) lb/yd³ 0-170 (60-170) lb/yd³ Fly Ash: ShaleFlue 0-141 (84.6-141) lb/yd³ 0-180 (60-180) lb/yd³ Dust: Mineral 0-101.5(56.4-101.5) lb/yd³ 0-170 (50-170 lb/yd³ Fines: Lime: 0-8.46 (5.64-8.46)lb/yd³ 0-12 (2.5-12) lb/yd³ CaSO₄ 2.82 (0-2.82) lb/yd³ 0-5 (2-5) lb/yd³(hemi): Design 0.42-0.47 0.38-0.50 w/cm: Actual 0.44-0.47 0.41-0.50w/cm: w/c: 0.59-0.68 0.55-0.75 w/p: 0.39-0.47 0.33-0.51

TABLE 4 Components (lb/yd³) Example (Mix ID) Compressive Strength 17D17E 17F 17G 17H Holcim II/V OPC 394.8 394.8 366.6 366.6 338.4 ClinkerReduction (%) 30% 30% 35% 35% 40% CO₂ reduction lb/yd³ 169.2 169.2 197.4197.4 225.6 Class F Fly Ash 112.8 112.8 141 112.8 141 Mine Rock Dust112.8 107.2 107.2 135.4 141 Type S Lime 0 5.64 5.64 5.64 5.64 CoarseAggregate 1720 1720 1750 1750 1750 Fine Aggregate 1260 1260 1237 12411241 Water 248.2 248.2 266.6 242.5 236.9 Design w/cm 0.44 0.44 0.47 0.440.43 Actual w/cm 0.49 0.48 0.52 0.50 0.49 w/c 0.63 0.63 0.73 0.66 0.70w/p 0.40 0.40 0.43 0.39 0.38  3-day (psi/MPa) 4320/29.8 4520/31.22850/19.6 4130/28.5 3180/21.9  7-day (psi/MPa) 5450/37.6 5900/40.13660/25.2 5330/36.7 4260/29.4 28-day (psi/MPa) 6830/47.1 7280/50.25320/36.7 6960/48.0 5930/40.9  3-month (psi/MPa) 8530/58.8 9300/64.16830/47.1 9080/62.6 8130/56.1  6-month (psi/MPa) 8750/60.3 9610/66.37540/52.0 9480/65.4 9100/62.7

Mixes 17D, 17E, 17F, 17G and 17H all appear to have benefitedsignificantly from including mineral fines as both a partial cementreplacement and a partial ultrafine aggregate addition. Mixes 17E, 17F,17G and 17H appear to have benefited by including Type S lime.

The foregoing compositions have the following characteristics andprophetic or hypothetical modification range:

Aspect Range Modification Range OPC: 366.6-394.8 lb/yd³ 320-450 lb/yd³Fly Ash/Pozzolan: 112.8-141 lb/yd³ 100-180 lb/yd³ Mineral Fines:112.8-141 lb/yd³ 80-180 lb/yd³ Lime: 0-5.64 (5.64) lb/yd³ 0-10 (3-10)lb/yd³ CaSO₄ (hemi): 0 lb/yd³ 0-5 (2-5) lb/yd³ Design w/cm: 0.43-0.470.39-0.51 Actual w/cm: 0.48-0.52 0.43-0.55 w/c: 0.63-0.73 0.58-0.80 w/p:0.38-0.43 0.33-0.48

TABLE 5 Components (lb/yd³) Example (Mix ID) Compressive Strength 17I17J 15-30-10 15-20-20 15-30-30 Holcim II/V OPC 366.6 338.4 394.8 394.8282 Clinker Reduction (%) 35% 40% 30% 30% 50% CO₂ reduction lb/yd³ 197.4225.6 169.2 169.2 282 Class F Fly Ash 141 0 0 0 0 Shale Flue Dust 0 141169.2 112.8 169.2 Mine Rock Dust 107.2 141 56.4 112.5 169.2 Type S Lime5.64 5.64 0 0 0 Coarse Aggregate 1750 1750 1745 1745 1745 Fine Aggregate1237 1241 1274 1274 1282 Water 242.5 236.9 265.1 265.1 253.8 Design w/cm0.43 0.43 0.45 0.47 0.47 Actual w/cm 0.47 0.49 0.47 0.52 0.56 w/c 0.660.70 0.67 0.67 0.90 w/p 0.39 0.38 0.43 0.43 0.41  3-day (psi/MPa)3360/23.2 3150/21.7 3390/23.4 3460/23.8 2130/14.7  7-day (psi/MPa)4360/30.1 4330/29.8 3900/26.7 3850/26.5 2700/18.6 28-day (psi/MPa)6190/42.7 6300/43.4 5190/35.8 5440/37.5 4000/27.6  3-month (psi/MPa)7430/51.2 7430/51.2 6080/41.9 5860/40.4 4240/29.2  6-month (psi/MPa)8400/57.9 7740/53.4 6240/43.0 6230/43.0 4290/29.6

Mixes 17I, 17J, 15-30-10, 15-20-20, and 15-30-30 all appear to havebenefited significantly from including mineral fines as both a partialcement replacement and a partial ultrafine aggregate addition. Mixes 17Iand 17J appear to have benefited by including Type S lime.

The foregoing compositions have the following characteristics andprophetic or hypothetical modification range:

Aspect Range Modification Range OPC: 282-394.8 lb/yd³ 270-450 lb/yd³ FlyAsh/Pozzolan: 0-141 (141) lb/yd³ 0-180 (100-180) lb/yd³ Shale Flue Dust:0-169.2 (112.8-169.2) lb/yd³ 0-200 (60-200) lb/yd³ Mineral Fines:56.4-169.2 (107.2-338.4) lb/yd³ 50-180 (80-350) lb/yd³ Lime: 0-5.64(5.64) lb/yd³ 0-10 (3-10) lb/yd³ CaSO₄ (hemi): 0 lb/yd³ 0-5 (2-5) lb/yd³Design w/cm: 0.43-0.47 0.39-0.51 Actual w/cm: 0.47-0.56 0.43-0.58 w/c:0.66-0.90  0.6-0.95 w/p: 0.39-0.43 0.33-0.48

TABLE 6 Components (lb/yd³) Example (Mix ID) Compressive Strength 14A14B 14AF 12CF 12CG Holcim II/V OPC 317.3 317.3 0 0 0 Fine Clinker, D90 =24 0 0 286.89 347.08 340.78 μm Clinker Reduction (%) 44% 44% 44% 35% 35%CO₂ reduction lb/yd³ 246.7 246.7 245.7 197.8 197.4 Class F Fly Ash 105.8211.6 105.75 0 0 UFFA 105.8 0 105.75 141 141 Coarse fly ash (CFA) 162.2268 162.15 0 0 Mine Rock Dust 105.8 0 105.8 104.34 104.34 Type S Lime14.1 14.1 14.1 8.46 8.46 Plaster of Paris 0 0 30.36 19.15 25.82 CoarseAggregate 800 800 0 0 0 Pea Gravel 800 800 1660 1750 1750 Fine Aggregate1263 1263 1210 1259 1257 Water 211.5 211.5 211.5 242.52 242.52 Designw/cm 0.28 0.26 0.24 0.43 0.43 Actual w/cm 0.30 0.26 0.26 0.47 0.47 w/c0.67 0.67 0.67 0.66 0.66 w/p 0.26 0.26 0.23 0.39 0.39  3-day (psi/MPa)4030/27.8 2950/20.3 3850/26.5 5209/35.9 5410/37.3  7-day (psi/MPa)5690/39.2 3790/26.1 5280/36.4 6850/47.2 6420/44.3 28-day (psi/MPa)9210/63.5 6170/42.5 8820/60.8 9980/68.8 9730/67.1  3-month (psi/MPa)10280/70.9  7110/49.0 11330/78.1  12460/85.9  12100/83.4   6-month(psi/MPa) 11510/79.4  8320/57.4 12820/88.4  13640/94.0  13910/95.9 

Mixes 14A, 14AF, 12CF, and 12CG all appear to have benefitedsignificantly from including mineral fines as both a partial cementreplacement and a partial ultrafine aggregate addition. Mixes 14A, 14B,14AF, 12CF, and 12CG appear to have benefited by including Type S lime.Mixes 14AF, 12CF, and 12CG appear to have benefited by including Fineclinker instead of OPC and UFFA instead of FA.

The foregoing compositions have the following characteristics andprophetic or hypothetical modification range:

Aspect Range Modification Range OPC: 317.3 lb/yd³ 280-480 lb/yd³ FineClinker: 286.89-347.08 lb/yd³ 250-450 lb/yd³ Fly Ash/Pozzolan: 0-211.6(105.8-211.6) lb/yd³ 0-250 (80-250) lb/yd³ Ultrafine Fly Ash: 0-141(105.8-141) lb/yd³ 0-170 (60-170) lb/yd³ Coarse Fly Ash: 0-268(162.2-268) lb/yd³ 0-300 (100-300) lb/yd³ Mineral Fines: 0-105.8(104.3-105.8) lb/yd³ 0-150 (50-200) lb/yd³ Lime: 8.46-14.1 lb/yd³ 0-20(5-20) lb/yd³ CaSO₄ (hemi): 0-30.36 (19.15-30.36) lb/yd³ 0-40 (15-40)lb/yd³ Design w/cm: 0.24-0.43 0.22-0.45 Actual w/cm: 0.26-0.47 0.24-0.50w/c: 0.66-0.67 0.62-0.72 w/p: 0.23-0.39 0.21-0.43

TABLE 7 Components (lb/yd³) Example (Mix ID) Compressive Strength 18A18B 18C 5A 5B Holcim II/V OPC 282 250.98 250.98 400 376 ClinkerReduction (%) 50% 55.5% 55.5% 29% 33.3% CO₂ reduction lb/yd³ 282 313 313164 188 GGBFS 0 250.98 250.98 0 0 Class F Fly Ash 197.4 0 0 0 361 MineRock Dust 152.28 112.8 109.98 400 112.8 Type S Lime 11.28 5.64 5.64 07.52 Plaster of Paris 5.64 0 2.82 4.0 7.52 Pea Gravel 1750 1750 17501500 1500 Fine Aggregate 1273 1348 1348 1190 1192 Water 242.5 242.5242.5 300 285.8 Design w/cm 0.43 0.43 0.43 0.50 0.35 Actual w/cm 0.490.48 0.48 0.75 0.38 w/c 0.86 0.97 0.97 0.75 0.76 w/p 0.37 0.39 0.39 0.380.33  3-day (psi/MPa) 1530/10.5 2170/15.0 4980/34.3 2980/20.5 4130/28.5 7-day (psi/MPa) 2700/18.6 5140/35.4 7080/48.8 3360/23.2 4860/33.528-day (psi/MPa) 4250/29.3 7510/51.8 8580/59.2 4000/27.6 7490/51.6 3-month (psi/MPa) 6380/44.0 7960/54.9 9570/66.0 4910/33.9 10000/68.9  6-month (psi/MPa) 7060/48.7 8050/55.5 9740/67.2 5250/36.2 11360/78.3 

Mixes 18A, 18B, 18C, 5A and 5B all appear to have benefitedsignificantly from including mineral fines as both a partial cementreplacement and a partial ultrafine aggregate addition. Mixes 18A, 18B,18C and 5B appear to have benefited by including Type S lime, and Mixes18A, 18C and 5B appear to have benefited by including plaster of Paris.In fact, the only difference between Mixes 18B and 18C was the inclusionof a small amount of plaster of Paris, with a corresponding reduction inmineral fines—the effect on strength was dramatic and consistent at allages, which indicates that the use of GGBFS in this mix caused a sulfatedeficit and the plaster of Paris apparently corrected it.

The foregoing compositions have the following characteristics andprophetic or hypothetical modification range:

Aspect Range Modification Range OPC: 250.98-400 lb/yd³ 220-450 lb/yd³GGBFS: 0-250.98 (250.98) lb/yd³ 250-450 lb/yd³ Fly Ash/ 0-361(197.4-361) lb/yd³ 0-400 (150-400) lb/yd³ Pozzolan: Mineral 109.98-400lb/yd³ 0-420 (80-420) lb/yd³ Fines: Lime: 0-11.28 (5.64-11.28) lb/yd³0-15 (3-15) lb/yd³ CaSO₄ 0-7.52 (2.82-7.52) lb/yd³ 0-10 (1.5-10) lb/yd³(hemi): Design 0.35-0.50 0.32-0.55 w/cm: Actual 0.38-0.75 0.35-0.85w/cm: w/c: 0.75-0.97 0.65-1.10 w/p: 0.33-0.39 0.30-0.45

TABLE 8 Components (lb/yd³) Example (Mix ID) Compressive Strength 19A19B 19C Holcim II/V OPC 250.98 250.98 480 Clinker Reduction (%) 55.5%55.5% 15% CO₂ reduction lb/yd³ 313 313 84 UFFA 250.98 250.98 200 MineRock Dust 107.16 104.34 200 Type S Lime 11.28 11.28 8 Plaster of Paris 02.82 8 Pea Gravel 1750 1750 1500 Fine Aggregate 1322 1321 1145 Water242.5 242.5 316.8 Design w/cm 0.43 0.43 0.40 Actual w/cm 0.47 0.47 0.46w/c 0.97 0.97 0.79 w/p 0.39 0.39 0.35  3-day (psi/MPa) 1420/9.8 1550/10.7 3890/26.8  7-day (psi/MPa) 2940/20.3 3170/21.9 5020/34.628-day (psi/MPa) 6650/45.9 6770/46.7 8680/59.8  3-month (psi/MPa)9740/67.2 9760/67.3 11020/76.0   6-month (psi/MPa) 11200/77.2 10280/70.9  11530/79.5 

Mixes 19A, 19B, and 19C all appear to have benefited significantly fromincluding mineral fines as both a partial cement replacement and apartial ultrafine aggregate addition and by including Type S lime. Theuse of plaster of Paris in Mix 19B does not seem to have made muchdifference, if any, and may have improved Mix 19C.

Aspect Range Modification Range OPC: 250.98-480 lb/yd³ 230-520 lb/yd³Ultrafine 200-250.98 lb/yd³ 140-300 lb/yd³ Fly Ash: Mineral 104.34-200lb/yd³ 80-250 lb/yd³ Fines: Lime: 8-11.28 lb/yd³ 0-15 (5-15) lb/yd³CaSO₄ 0-8 (2.82-8) lb/yd³ 0-12 (1.5-12) lb/yd³ (hemi): Design w/cm:0.40-0.43 0.37-0.48 Actual w/cm: 0.46-0.47 0.40-0.52 w/c: 0.79-0.970.65-1.10 w/p: 0.35-0.39 0.30-0.45

Concrete Mixes: Design Strength=5000 psi (34.5 MPa) @ 28 Days

The following examples were designed and manufactured according to thepresent invention and are based on a commercial mix of a U.S. concretecompany having a design strength of 5000 psi (34.5 MPa) at 28 days andtotal cementitious binder of 610 lbs/yd³. The compositions, strengths,and estimated cost savings are set forth below in Table 9. All mixesexceeded the design strength and had reduced cost compared to thecommercial mix.

TABLE 9 Components (lb/yd³) Example (Mix ID) Compressive Strength 1A 1B1C 1D 1E Lehigh II/V OPC 197.4 225.5 213.5 213.5 198.25 ¹ ClinkerReduction (%) 35% 26% 30% 30% 35% ² CO₂ reduction lb/yd³ 89.4 66.0 75.975.9 88.6 Lehigh GGBFS 197.4 225.5 213.5 183 198.25 Class F Fly Ash 84.60 91.5 91.5 91.5 Limestone Powder 132.54 145.75 152.5 183 177.5 Type SLime 5.64 5.5 0 0 3.05 Plaster of Paris 2.86 2.75 0 0 2.44 CoarseAggregate 1750 1800 1700 1700 1750 Fine Aggregate 1440 1484 1386 13851320 Water 253.8 247.5 274.5 274.5 274.5 Design w/cm 0.45 0.45 0.45 0.450.45 Actual w/cm 0.52 0.54 0.53 0.56 0.56 w/c 1.29 1.10 1.29 1.29 1.38w/p 0.41 0.41 0.41 0.41 0.41 Cost reduction $/yd³ $2.96 $1.91 $2.38$3.17 $2.99  3-day (psi/MPa) 2210/15.2 1940/13.4 1970/13.6 1970/13.61820/12.5  7-day (psi/MPa) 3670/25.3 3550/24.5 3770/26.0 3600/24.83430/23.6 28-day (psi/MPa) 5720/39.4 5540/38.2 6380/44.0 6560/45.25680/39.2  3-month (psi/MPa) 6170/42.5 6560/45.2 7460/51.4 7240/49.96480/44.7  6-month (psi/MPa) 6930/47.8 7220/49.8 7820/53.9 8130/56.06820/47.0 ¹ clinker reduction compared to OPC in commercial mix ²Assumes 0.83 ton of CO₂ emitted per ton of cement manufactured pcy = percubic yard

The use of mineral fines, i.e., limestone powder (Blue Mountain MineralsFeed Flour) according to the invention permitted substantial clinkerreduction, cost reduction, and comparable strength compared tocommercial mix. Type S lime and plaster of Paris appear to have anegative effect in these mixes, suggesting that at higher w/c they arenot necessarily beneficial.

The foregoing compositions have the following characteristics andprophetic or hypothetical modification range:

Aspect Range Modification Range OPC: 197.4-225.5 lb/yd³ 150-275 lb/yd³GGBFS: 183-225.5 lb/yd³ 120-250 lb/yd³ Fly Ash: 0-91.5 (84.6-91.5)lb/yd³ 0-150 (50-150) lb/yd³ Mineral Fines: 132.5-183 lb/yd³ 100-220lb/yd³ Design w/cm: 0.45 0.42-0.48 Actual w/cm: 0.52-0.56 0.48-0.60 w/c:1.10-1.38 0.90-1.60 w/p: 0.41 0.37-0.45

Concrete Mixes: Design Strength=8000 psi (55.2 MPa) @ 28 Days

The following examples were designed and manufactured according to thepresent invention and are based on a commercial mix of a U.S. concretecompany having a design strength of 8000 psi (55.2 MPa) at 28 days andtotal cementitious binder of 845 lbs/yd³. The compositions, strengths,and estimated cost savings are set forth below in Tables 10 and 11. Allmixes exceeded the design strength and had reduced cost compared to thecommercial mix.

TABLE 10 Components (lb/yd³) Example (Mix ID) Compressive Strength 2A 2C2D 2E 2F Lehigh II/V OPC 295.75 297.5 297.5 297.5 297.5 ¹ ClinkerReduction (%) 30% 30% 30% 30% 30% ² CO₂ reduction lb/yd³ 105.6 104.2104.2 104.2 104.2 Lehigh GGBFS 295.75 297.5 297.5 297.5 297.5 Class FFly Ash 126.75 0 0 0 0 Limestone Powder 211.25 210 203 203 199.5 Type SLime 0 0 7 0 7 Plaster of Paris 0 0 0 7 3.5 Coarse Aggregate 1600 17001700 1700 1700 Fine Aggregate 1225 1392 1391 1392 1390 Water 283.2 252252 252 252 Design w/cm 0.34 0.36 0.36 0.36 0.36 Actual w/cm 0.39 0.420.42 0.42 0.42 w/c 0.96 0.85 0.85 0.85 0.85 w/p 0.30 0.31 0.31 0.31 0.31Cost reduction $/yd³ $2.41 $7.79 $7.46 $7.45 $6.53  3-day (psi/MPa)5370/37.0 4750/32.7 4540/31.3  5960/41.1  6870/47.4  7-day (psi/MPa)7780/53.6 6900/47.6 6320/43.6  8680/59.8  9080/62.6 28-day (psi/MPa)9330/64.3 9110/62.8 7970/55.0 10360/71.4 10900/75.5  3-month (psi/MPa)10210/70.4  9400/64.8 N/A 11390/78.5 11610/80.0  6-month (psi/MPa)11230/77.4  9870/68.1 N/A 11440/78.9 12060/83.2 ¹ clinker reductioncompared to OPC in commercial mix ² Assumes 0.83 ton of CO₂ emitted perton of cement manufactured pcy = per cubic yard

Mixes 2C-2F are virtually identical except for varying quantities ofType S lime and plaster of Paris. The best results were obtained whenplaster of Paris was used Type S lime provided no benefit by itself anda small benefit when used in combination with plaster of Paris. Itappears that more Type S lime than could be consumed was added given thelow w/cm of the mixes and low solubility of lime.

TABLE 11 Components (lb/yd³) Example (Mix ID) Compressive Strength 2F-12F-2 2G 2H 2H-1 Lehigh II/V OPC 297.5 297.5 270 294.5 294.5 ¹ ClinkerReduction (%) 30% 30% 36% 30% 30% ² CO₂ reduction lb/yd³ 104.2 104.2 127106.7 106.7 Lehigh GGBFS 297.5 297.5 270 259 259 Class F Fly Ash 0 0100.5 70 0 Huntington UFFA 0 0 0 0 70 Limestone Powder 199.5 199.5 175.5171.5 171.5 Type S Lime 7 7 6 7 7 Plaster of Paris 3.5 3.5 3 3.5 3.5Coarse Aggregate 1700 1700 1650 1650 1650 Fine Aggregate 1366 1390 13301409 1429 Water 252 252 270 252 252 Design w/cm 0.36 0.36 0.36 0.36 0.36Actual w/cm 0.42 0.42 0.42 0.40 0.40 w/c 0.85 0.85 1.00 0.83 0.83 w/p0.31 0.31 0.33 0.31 0.31 Cost reduction $/yd³ $6.11 $7.46 $7.65 $9.56$7.67  3-day (psi/MPa) 2900/20.0 4335/29.9 4570/31.5  3385/23.3 3845/26.5  7-day (psi/MPa) 5580/38.5 7680/53.0 6460/44.5  6150/42.4 6835/47.1 28-day (psi/MPa) 8180/56.4 9820/67.7 9080/62.6 10600/73.110380/71.6  3-month (psi/MPa) 9290/68.9 12920/89.1  9870/68.1 11280/77.812580/86.7  6-month (psi/MPa) 11070/76.3  N/A 11080/76.4  N/A N/A ¹clinker reduction compared to OPC in commercial mix ² Assumes 0.83 tonof CO₂ emitted per ton of cement manufactured pcy = per cubic yard

Mixes 2C-2F are virtually identical except for varying quantities ofType S lime and plaster of Paris. The best results were obtained whenplaster of Paris was used. Type S lime provided no benefit by itself andmore early than later benefit when used in combination with plaster ofParis. Given the low w/cm of the mixes and low solubility of lime,perhaps more Type S lime than could be consumed was added and some endedup unreacted.

Mix 2F was tested for shrinkage by Central Concrete, which indicatedless than 0.070% shrinkage at 28 days, and lower shrinkage at each of 7,14, 21, and 28 days than a control mix based on the correspondingcommercial mix.

The foregoing compositions have the following characteristics andprophetic or hypothetical modification range:

Aspect Range Modification Range OPC: 270-297.5 lb/yd³ 250-395 lb/yd³GGBFS: 259-297.5 lb/yd³ 200-350 lb/yd³ Fly Ash: 0-126.75 (70-126.75)lb/yd³ 0-180 (50-180) lb/yd³ Mineral 171.5-211.25 lb/yd³ 125-275 lb/yd³Fines: Lime: 0-7 (6-7) lb/yd³ 0-12 (3-12) lb/yd³ CaSO₄ 0-7 (3-7) lb/yd³0-12 (3-12) lb/yd³ (hemi): Design 0.34-0.36 0.31-0.40 w/cm: Actual0.39-0.42 0.35-0.48 w/cm: w/c: 0.83-1.00 0.70-1.20 w/p: 0.30-0.330.26-0.38

Concrete Mixes: Design Strength=4000 psi (27.6 MPa) @ 3 Days

The following examples were designed and manufactured according to thepresent invention and are based on a commercial mix of a U.S. concretecompany with a design strength of 4000 psi (27.6 MPa) at 3 days andtotal cement binder of 687 lbs/yd³. The compositions, strengths, andestimated cost savings are set forth below in Table 12. All mixesequaled or exceeded the design strength and all had reduced costcompared to the commercial mix.

TABLE 12 Components (lb/yd³) Example (Mix ID) Compressive Strength 18C3A 3B 3B-1 3C Lehigh II/V OPC 250.98 343.5 267 267 287.1 ¹ ClinkerReduction (%) 63% 50% 61% 61% 35% ² CO₂ reduction lb/yd³ 361.9 285.1348.6 348.6 331.9 Lehigh GGBFS 250.98 206.1 267 267 287.1 LimestonePowder 109.98 206.1 117 117 141.9 Type S Lime 5.64 0 6 6 6.6 Plaster ofParis 2.82 0 3 3 3.3 Coarse Aggregate 1800 1700 1800 1800 1750 FineAggregate 1468 1369 1452 1440 1376 Water 242.5 274.9 240 240 264 Designw/cm 0.43 0.40 0.40 0.40 0.40 Actual w/cm 0.48 0.50 0.44 0.44 0.45 w/c0.97 0.80 0.90 0.90 0.92 w/p 0.39 0.36 0.36 0.36 0.41 Cost reduction$/yd³ $5.87 $4.64 $6.12 $8.54 $4.17  3-day (psi/MPa) 5170/35.6 4010/27.64750/13.6 4160/28.7 4620/31.8  7-day (psi/MPa) 7010/48.3 6010/41.46930/47.8 5890/40.6 6820/47.0 28-day (psi/MPa) 8790/60.6 8280/57.19060/62.5 8420/58.0 9290/64.0  3-month (psi/MPa) 9910/68.3 8950/61.710200/70.3  9870/68.1 10110/69.7   6-month (psi/MPa) 10540/72.7  N/A N/AN/A 10600/73.1  ¹ clinker reduction compared to OPC in commercial mix ²Assumes 0.83 ton of CO₂ emitted per ton of cement manufactured pcy = percubic yard

The use of mineral fines (limestone powder) according to the inventionpermitted substantial clinker reduction, cost reduction, and comparablestrength compared to commercial mix. Type S lime and plaster of Parisappear to provide a positive effect in these mixes, perhaps because theywere appropriate for the w/c.

Mixes 18C-1, 3B, and 3C were tested for shrinkage by Central Concrete,which indicated less than 0.040% shrinkage at 28 days for each mix, andlower shrinkage for each mix at each of 7, 14, 21, and 28 days than acontrol mix based on the corresponding commercial mix.

The foregoing compositions have the following characteristics andprophetic or hypothetical modification range:

Aspect Range Modification Range OPC: 250.98-343.5 lb/yd³ 230-500 lb/yd³GGBFS: 259-297.5 lb/yd³ 150-350 lb/yd³ Mineral Fines: 109.98-206.1lb/yd³ 90-250 lb/yd³ Lime: 0-6.6 (5.64-6.6) lb/yd³ 0-10 (3-10) lb/yd³CaSO₄ (hemi): 0-3.3 (2.82-3.3) lb/yd³ 0-7 (1.5-7) lb/yd³ Design w/cm:0.40-0.43 0.35-0.48 Actual w/cm: 0.44-0.50 0.40-0.55 w/c: 0.80-0.970.55-1.05 w/p: 0.36-0.41 0.33-0.46

Concrete Mixes: Design Strength=4000 psi (27.6 MPa) @ 28 Days

The following examples were designed and manufactured according to thepresent invention and are based on a commercial mix of a U.S. concretecompany with a design strength of 4000 psi (27.6 MPa) at 28 days andtotal cement binder of 551 lbs/yd³. The compositions, strengths, andestimated cost savings are set forth below in Table 13. All mixesequaled or exceeded the design strength and all had reduced costcompared to the commercial mix.

TABLE 13 Components (lb/yd³) Example (Mix ID) Compressive Strength 4A 4B4C 4D 4F Lehigh II/V OPC 198.4 192.9 275.5 250 208 ¹ Clinker Reduction(%) 34% 36% 9% 17% 31% ² CO₂ reduction lb/yd³ 86.8 91.4 22.8 44.0 78.9Lehigh GGBFS 198.4 176.3 176.3 175 156 Class F Fly Ash 74.1 74.1 55.1 078 Limestone Powder 132.2 159.8 137.75 125 130 Coarse Aggregate 16751675 1700 1750 1680 Fine Aggregate 1428 1426 1418 1511 1518 Water 273273 273 248 250 Design w/cm 0.50 0.50 0.50 0.50 0.50 Actual w/cm 0.580.62 0.54 0.58 0.57 w/c 1.38 1.42 0.99 0.99 1.20 w/p 0.45 0.45 0.45 0.450.44 Cost reduction $/yd³ $1.41 $2.15 $0.76 $1.03 $1.01  3-day (psi/MPa)2010/13.8 1760/12.1 1860/12.8 1920/13.2 1770/12.2  7-day (psi/MPa)3310/22.8 3120/21.5 3280/22.6 3270/22.5 3200/22.1 28-day (psi/MPa)6480/44.7 5230/36.0 5890/40.6 5890/40.6 5430/37.4 ¹ clinker reductioncompared to OPC in commercial mix ² Assumes 0.83 ton of CO₂ emitted perton of cement manufactured pcy = per cubic yard

The use of mineral fines (limestone powder) according to the inventionpermitted substantial clinker reduction, cost reduction, and comparablestrength compared to commercial mix. Type S lime and plaster of Pariswere not used.

The foregoing compositions have the following characteristics andprophetic or hypothetical modification range:

Aspect Range Modification Range OPC: 198.4-275.5 lb/yd³ 150-335 lb/yd³GGBFS: 156-198.3 lb/yd³ 100-250 lb/yd³ Fly Ash: 0-78 (55.1-78) lb/yd³0-140 (40-140) lb/yd³ Mineral Fines: 125-159.8 lb/yd³ 100-225 lb/yd³Design w/cm: 0.50 0.47-0.54 Actual w/cm: 0.54-0.62 0.50-0.67 w/c:0.99-1.42 0.85-1.60 w/p: 0.45 0.42-0.48

Working Examples—Ready Mixed Concrete Field Test

In cooperation with a ready mixed concrete company in Salt Lake City,Utah, the inventor made 10 concrete mixes and had them delivered to ajob site in standard ready mixed concrete trucks to confirm whether theconcrete mixes disclosed herein can be readily scaled up, mixed,delivered, finished, and cured like conventional concrete. All mixesbehaved adequately and produced quality concrete of acceptable slump,strength, finishability, and set time. The mixes were loosely designedto replace a standard concrete mix design containing OPC (553 lb/yd³)and fly ash (115 lb/yd³) cementitious binder, with a design strength of4500 psi @ 28 days. A portion of concrete from the concrete mixer truckwas taken off and cast into 4×8 inch cylinders for compressive strengthtesting by CMT Engineering.

The mix designs and properties are set forth below in Tables 14 and 15.While not all mixes had 28-day compressive strength of 4500 psi, themargin of cost savings was so great that they can easily be redesignedto have greater strength while still reducing cost.

TABLE 14 Components (lb/yd³) Roman Cement Mix ID Compressive StrengthRM-1 RM-2 RM-3 RM-4 RM-5 Type II/V OPC 396.49 396.49 365.98 500 390 ¹Percent OPC Reduction 28.3% 28.3% 33.8% 10% 29.5% ² CO₂ reduction lb/yd³129.9 129.9 155.2 44 135.3 Fly Ash 122 0 91.5 0 130 Shale Flue Dust 0122 91.5 125 130 Coal Mine Rock Dust 143.35 125.3 74.49 0 0 Type S Lime6.10 6.10 6.10 0 0 Plaster of Paris 3.06 3.06 4.59 0 0 Coarse Aggregate1650 1675 1675 1675 1650 Fine Aggregate 1287.9 1256 1260 1258.5 1217Water 280.6 274.5 274.5 291.25 292.50 ³ Design mix w/cm 0.46 0.45 0.450.466 0.45 ⁴ Actual w/cm 0.53 0.52 0.49 0.466 0.45 w/c 0.69 0.677 0.7290.583 0.75 w/p 0.42 0.422 0.432 0.466 0.45 Cost reduction $/yd³ $6.55$11.99 $10.73 $7.80 $9.18  3-day (psi/MPa) 1900/13.1 1700/11.7 1970/13.62310/15.9 1590/11.0  7-day (psi/MPa) 3050/21.0 2500/17.2 2730/18.83300/22.8 2600/17.9 28-day (psi/MPa) 4220/29.1 3450/23.8 4280/29.54720/32.5 4200/29.0 56-day (psi/MPa) 4650/31.4 4185/28.9 5175/35.7 5170/35.65 4830/33.3 ¹ OPC reduction compared to commercial mix ²Assuming 0.83 ton of CO₂ emitted per ton of cement manufactured ³ Designw/cm assumes a portion of coal mine rock dust is “cementitious binder” ⁴Actual w/cm excludes coal mine rock dust from the “cementitious binder”

The foregoing compositions have the following characteristics andprophetic or hypothetical modification range:

Aspect Range Modification Range OPC: 366-500 lb/yd³ 300-550 lb/yd³ FlyAsh: 0-130 (91.5-130) lb/yd³ 0-200 (50-200) lb/yd³ Shale Flue Dust:0-130 (91.5-130) lb/yd³ 0-200 (50-200) lb/yd³ Mineral Fines: 0-143(74.5-143) lb/yd³ 0-225 (50-225) lb/yd³ Lime: 0-6.1 lb/yd³ 0-10 (3-10)lb/yd³ CaSO₄ (hemi): 0-4.6 (3-4.6) lb/yd³ 0-7 (1.5-7) lb/yd³ Designw/cm: 0.45-0.466 0.42-0.48 Actual w/cm: 0.45-0.53  0.42-0.58 w/c:0.583-0.75  0.55-0.90 w/p: 0.42-0.466 0.38-0.48

TABLE 15 Components (lb/yd³) Roman Cement Mix ID Compressive StrengthRM-6 RM-7 RM-8 RM-9 RM-10 Type II/V OPC 454.98 337.48 429 396.5 405 ¹Percent OPC Reduction 18% 39% 22.4% 28.3% 26.8% ² CO₂ reduction lb/yd³81.4 179 103 130 123 GGBFS 0 225 0 0 0 Fly Ash 70 112.5 102 61 0 FineFly Ash 0 0 0 115.9 0 Ultrafine Fly Ash 105 0 0 0 0 Limestone-VolcanicAsh 0 0 125.72 0 0 Shale Flue Dust 0 0 0 0 264.94 Coal Mine Rock Dust126 127.5 0 61 0 Type S Lime 3.50 5.63 1.65 3.05 1.69 Plaster of Paris3052 5.65 1.65 3.05 3.37 Coarse Aggregate 1650 1625 1675 1675 1700 FineAggregate 1168 1127 1215 1263 1200 Water 294 300 283.8 274.5 283.50 ³Design mix w/cm 0.42 0.40 0.43 0.45 0.42 ⁴ Actual w/cm 0.462 0.437 0.430.474 0.42 w/c 0.636 0.860 0.657 0.682 0.691 w/p 0.385 0.369 0.430 0.4290.42 Cost reduction/yd³ <$2.65> <$3.62> $0.92 $3.68 $11.35  3-day(psi/MPa) 2680/18.5 3050/21.0 1750/12.1 2290/15.8 1800/12.4  7-day(psi/MPa) 3820/26.3 4720/32.7 2500/17.2 3050/21.0 2430/16.8 28-day(psi/MPa) 6600/45.5 6120/42.2 3900/26.9 3905/26.9 4220/29.1 91-day(psi/MPa) n/a/n/a n/a/n/a n/a/n/a n/a/n/a n/a/n/a  6-month (psi/MPa)n/a/n/a n/a/n/a n/a/n/a n/a/n/a n/a/n/a ¹ OPC reduction compared tocommercial mix ² Assuming 0.83 ton of CO₂ emitted per ton of cementmanufactured ³ Design w/cm assumes a portion of coal mine rock dust is“cementitious binder” ⁴ Actual w/cm excludes coal mine rock dust fromthe “cementitious binder”

The foregoing compositions have the following characteristics andprophetic or hypothetical modification range:

Aspect Range Modification Range OPC: 337.5-455 lb/yd³ 300-550 lb/yd³GGBFS: 0-255 (255) lb/yd³ 0-350 (150-350) lb/yd³ Fly Ash: 0-112.5(61-112.5) lb/yd³ 0-200 (50-200) lb/yd³ Fine Fly 0-115.9 (115.9) lb/yd³0-175 (40-175) lb/yd³ Ash: Ultrafine 0-105 (105) lb/yd³ 0-150 (35-150)lb/yd³ Fly Ash: Shale Flue 0-265 (265) lb/yd³ 0-350 (100-350) lb/yd³Dust: LS-Volcanic 0-125.72 (125.72) lb/yd³ 0-200 (50-200) lb/yd³ Ash:Mineral 0-127.5 (61-127.5) lb/yd³ 0-200 (50-200) lb/yd³ Fines: Design 0.40-0.45 0.37-0.47 w/cm: Actual  0.42-0.474 0.40-0.50 w/cm: w/c:0.636-0.86 0.60-1.00 w/p: 0.369-0.43 0.33-0.46

The purpose of the foregoing mixes was not to reduce cost per se but totest a variety of supplementary cementitious materials (SCMs) to see howconcrete would behave in a concrete mixertruck. The first two mixes hadsubstantially greater strength than 4500 psi with only minor costincrease compared to the 4500 psi control mix. The second two mixes usedleftover SCMs in the inventor's possession. The last mix had very highsubstitution of OPC with shale flue dust. Given the high cost saving, itcan easily be redesigned to have higher strength if required.

Comparative Example—Carbon Injection Technology

As of 2018, one of the most highly touted technologies for reducing thecarbon footprint of concrete, measured as reduction of CO₂ per cubicyard, involves injecting CO₂ into freshly mixed concrete. This is toutedto reduce the CO₂ footprint of concrete in two ways: (1) injected CO₂reacts with lime (CaO) to form insoluble calcium carbonate (CaCO₃) and(2) the calcium carbonate marginally increases strength, permitting asmall Portland cement reduction. According to numbers published by aleading CO₂ injection company, total reduction of CO₂ is reportedly11.44 pounds per cubic yard (lb/pcy). The net cost reduction using thisprocess is reportedly $0.94 pcy. This is the current state of the artfor CO₂ reduction and cost savings.

By comparison, the CO₂ reduction for concrete mixes based on thecommercial mix having a design strength of 5000 psi (34.5 MPa) at 28days and total cementitious binder of 610 lbs/yd³ (Examples 1A to 1E)was between 66.0 and 89.4 lb/pcy. These mixes provided 6 to 8 times moreCO₂ reduction than CO₂ injection. The net cost saving for these mixeswas between $1.91 and $3.17 pcy, about 2 to 3 times more than for CO₂injection.

By further comparison, the CO₂ reduction for concrete mixes based on thecommercial mix having a design strength of 8000 psi (55.2 MPa) at 28days and total cementitious binder of 845 lbs/yd³ (Examples 2A to 2H-1)was between 104.2 and 127 lb/pcy. These examples provided 9 to 11 timesmore CO₂ reduction than CO₂ injection. The net cost saving for thesemixes was between $2.41 and $9.56 pcy, about 2½ to 10 times more thanfor CO₂ injection.

By further comparison, the CO₂ reduction for concrete mixes based on thecommercial mix having a design strength of 4000 psi (27.6 MPa) at 3 daysand total cementitious binder of 687 lbs/yd³ (Examples 18C to 3C) wasbetween 285.1 and 361.9 lb/pcy. These mixes provided 25 to 31 timesgreater CO₂ reduction than CO₂ injection. The net cost saving for thesemixes was between $4.64 and $8.54 pcy, about 5 to 9 times more than forCO₂ injection.

By further comparison, the CO₂ reduction for concrete mixes based on thecommercial mix having a design strength of 4000 psi (27.6 MPa) at 28days and total cementitious binder of 551 lbs/yd³ (Examples 4A to 4F)was between 22.8 and 91.4 lb/pcy. These mixes provided 2 to 8 timesgreater CO₂ reduction than CO₂ injection. The net cost saving for thesemixes was between $0.76 and $2.15 pcy, or up to twice the cost savingsof CO₂ injection.

Working Examples—Mortar

Mortar mixes were made according to ASTM C109 using a Hobart mixer butwere modified to include less water and more cement. Fresh mortar wascast into 2×2 inch cubes and tested by CMT Engineering in West ValleyCity, Utah. Portland cement was a Type I/II OPC manufactured by Holcim,Devil's Slide, Utah plant, and purchased at Home Depot, Salt Lake City.Ultrafine fly ash (UFFA) was made by classifying a fly ash fromHuntington, Hunter, Jim Bridger, and Gaston power plants. The Bridgerfly ash was moist, became agglomerated and did not form UFFA but eitherthere was no separation or there was only poor separation. It will bedesignated as fine fly ash (FFA). The silica fume was condensed silicafume provided by Calmetrix. The calcined shale dust was obtained fromUtelite, Coalville, Utah. Class F fly ash was a standard fly ashobtained from Gaston, Ala., steam power plant owned by Boral andprovided by its predecessor Headwaters Inc., of South Jordan, Utah.Limestone powder was Marble White 80 from Specialty Minerals. Themineral fines containing about 90% limestone as calcite was coal minerock dust purchased from Staker Parson and produced in Genola, Utah atKeigley limestone quarry. The sand was graded Unimin silica sandpurchased at Home Depot. The components, their quantities, andcompressive strengths of the mortar mixes are set forth in Tables 14-22.Lignosulfonate (Plastocrete 161) and/or polycarboxylate ether(Viscocrete 2100) were used in some cases to maintain flow between100-120 on a flow table.

Mix 111 is a 100% OPC control mix. Mix 111A is an 85-15% OPC-fly ashcontrol mix. Mix 111B is an 85-15% OPC-silica fume control mix. They aresurrogates for how concrete and mortar are commonly manufactured. Mix111 illustrates a high strength mortar that includes an elevatedquantity of OPC and has a moderately low water to cement ratio(w/c=0.35). Mix 111A illustrates the negative effect on early strengthof replacing 15% of the OPC with ordinary fly ash. Mix 111B illustratesthe positive effect on strength of replacing 15% of the OPC with silicafume. The effect on strength of using different SCMs and optionallymineral fines and/or Type S lime, are illustrated by the other mortarmixes below.

TABLE 16 Components/ Compressive Example (Mix ID) Strength 111 111A 111B111D 111E 111F Type I/II OPC (g) 920 782 782 782 782 782 Gaston Fly Ash(g) 0 138 0 0 0 0 Silica Fume (g) 0 0 138 0 0 0 Hunter UFFA (g) 0 0 0138 0 0 Bridger Fly Ash (g) 0 0 0 0 138 0 Huntington UFFA (g) 0 0 0 0 0138 Silica Sand (g) 1925 1883 1883 1883 1880 1880 Water (g) 322 322 322322 322 322 w/c 0.35 0.41 0.41 0.41 0.41 0.41 w/cm 0.35 0.35 0.35 0.350.35 0.35  3-day (psi/MPa) 8358/57.6 7135/49.2 7560/52.1 6630/45.76327/43.6 8045/55.5  7-day (psi/MPa) 8770/60.5 8300/57.2 9687/66.88167/56.3 7690/53.0 8827/60.9 28-day (psi/MPa) 11425/77.8 8895/61.312337/85.1 9192/63.4 8677/59.8 12920/89.1

Mixes 111A and 111E indicate that using unprocessed Gaston fly ash andpoorly classified Bridger fly ash yielded mortar having substantiallyreduced strength compared to Mix 111. Mixes 111D and 111F indicate thatHunter and Huntington UFFA were substantially superior to Gaston andBridger fly ashes. Huntington UFFA was comparable to silica fume interms of strength development but required significantly lesssuperplasticizer to yield mortar with proper flow.

TABLE 17 Components/ Compressive Example (Mix ID) Strength 111G 111H111I 111J 111K 111L Type I/II OPC (g) 782 782 782 782 782 782 BridgerFFA (g) 138 138 138 138 0 0 Gaston UFFA (g) 0 0 0 0 138 0 Gaston FFA (g)0 0 0 0 0 138 Marble White 80 (g) 0 0 138 138 138 138 Quicklime (g)13.92 0 0 0 0 0 Type S Lime (g) 0 18.4 0 0 0 0 Silica Sand (g) 1851 18511622 1747 1747 1747 Water (g) 332.92 328.44 322 322 322 322 w/cm 0.350.35 0.35 0.35 0.35 0.35  3-day (psi/MPa) 7202/49.6 7785/53.4 8067/55.68442/58.2 7712/53.2 6760/46.6  7-day (psi/MPa) 8595/59.3 8165/56.39000/62.0 10075/69.5 9362/64.5 8375/57.7 28-day (psi/MPa) 11035/76.110755/71.1 11387/78.5 10960/75.6 11477/79.1 10542/72.7

Mixes 111G and 111H indicate that using lime as an additive to Bridgerfly ash substantially improved strength at all ages. Mixes 111I-111Lindicate that using mineral fines (limestone powder) improved thestrength of mortars containing Bridger fly ash, Gaston UFFA or GastonFFA.

TABLE 18 Components/ Compressive Example (Mix ID) Strength 111M 111N111O 111P 111Q 111R Type I/II OPC (g) 782 782 782 782 782 782 BridgerFFA (g) 138 0 0 0 0 0 Huntington UFFA (g) 0 138 138 138 0 0 CalcinedShale Dust (g) 0 0 0 0 138 138 Marble White 80 (g) 138 0 138 138 0 0Type S Lime (g) 9.2 18.4 0 18.4 18.4 0 Silica Sand (g) 1722 1851 17471722 1851 1883 Water (g) 325.22 322 322 322 322 322 w/cm 0.35 0.35 0.350.35 0.35 0.35  3-day (psi/MPa) 7935/54.7 8225/56.7 8212/56.6 7445/51.37145/49.3 4507/31.1  7-day (psi/MPa) 10225/70.5 9570/66.0 8890/61.39080/62.6 8205/56.6 8235/56.8 28-day (psi/MPa) 11750/81.0 10050/69.311295/77.9 11297/77.9 10247/70.6 10000/68.9

Mixes 111M-111P show the effect on strength of using mineral fines(limestone powder) and/or lime on strength when using different types offly ash. Mixes 111Q and 111R illustrate the effect of using or not usinglime when using calcined shale dust. When lime is used, the mortarcontaining calcined shale dust exhibited much higher 3-day strength,similar 7-day strength, and slightly higher 28-day strength.

TABLE 19 Components/ Compressive Example (Mix ID) Strength 111S 111T111U 111V 111W 111X Type I/II OPC (g) 644 644 644 782 782 782 BridgerFFA (g) 138 138 138 138 0 138 Huntington UFFA (g) 0 0 0 0 0 0 CalcinedShale Dust (g) 138 138 138 0 138 0 Marble White 80 (g) 0 138 138 0 0 0Mine Rock Dust (g) 0 0 0 138 138 138 Type S Lime (g) 0 0 18.4 0 0 9.2Silica Sand (g) 1841 1698 1678 1764 1764 1732 Water (g) 322 322 322 322322 325.22 w/cm 0.35 0.35 0.35 0.35 0.35 0.35  3-day (psi/MPa) 6020/41.56175/42.6 6670/46.0 8647/59.6 6877/47.4 8882/61.2  7-day (psi/MPa)7390/50.9 6922/47.7 7575/52.2 9695/66.8 8735/60.2 9535/65.7 28-day(psi/MPa) 9120/62.9 8985/61.9 9985/68.8 11492/79.2 10455/72.1 10925/75.3

Mixes 111S-111U demonstrate the effect of substituting twice as much OPC(i.e., 30%) with Bridger fly ash and calcined shale dust, optionallywith limestone powder. Mixes 111V-111X demonstrate the beneficial effecton strength of using finer mineral fines instead of coarser limestonepowder. Mixes 111W and 111X compare the effect of excluding or includinglime when using quarry dust and calcined shale or FFA.

TABLE 20 Components/Compressive Example (Mix ID) Strength 111Y 111Z TypeI/II OPC (g) 782 782 Huntington UFFA (g) 138 0 UF Steel Slag (g) 0 138Mine Rock Dust (g) 138 138 Type S Lime (g) 9.2 9.2 Silica Sand (g) 17321776 Water (g) 325.22 325.22 w/cm 0.35 0.35  3-day (psi/MPa) 8605/59.38475/58.4  7-day (psi/MPa) 9755/67.2 9742/67.2 28-day (psi/MPa)11990/82.7  11415/78.7 

Mixes 111Y and 111Z show the effect of using mineral fines and lime toassist the strength development of mortar made using either UFFA orultrafine steel slag, which is an industrial waste product having fewuses and that is not used effectively in mortar and concrete by theindustry. Mix 111Z shows that even very inexpensive steel slag, whenblended with mineral fines and lime, can produce mortar comparable instrength to mortars made using UFFA and silica fume.

Working Examples—Architectural Cast Stone

Architectural cast stone mixes were made based on a commercial mixdesign that used Portland White Cement, three differently sizedlimestone aggregates (Specialty Minerals #9 coarse limestone sand, Vical1600 medium limestone sand, and Marble White 80 fine limestoneaggregate/coarse limestone powder), latex adhesive to bond topolystyrene foam, polyvinyl acetate (PVA) fibers to increase toughness,superplasticizer to maintain low water to cement ratio (e.g., w/c=0.36),and viscosity modifying agent (cellulosic either) to prevent segregationand assist fiber dispersion. Mix 104 was a mortar mix derived from acommercial cast stone mix, used white cement as sole cementitiousbinder, and is the control mix. Mixes 104A-104D were designed by theinventor to provide a similarly commercially acceptable cast stone mixbut with substantially reduced cement clinker content and lower cost(i.e., about 10-20% less expensive in material cost compared to thecommercial mix design).

White cement, aggregates, fiber, adhesive, superplasticizer, andviscosity modifying agent were provided by Tuscan Stoneworx, Lindon,Utah. GGBFS was white or off-white and purchased from Lehigh Cement,Stockton, Calif. Fine recycled glass was baghouse glass provided byMomentum Recycling in Salt Lake City, Utah. Type S lime was purchasedfrom Home Depot, Salt Lake City, Utah. Fine limestone powder is anagricultural limestone purchased from Oldcastle.

TABLE 21 Components/Compressive Example (Mix ID) Strength 104 104A 104B104C 104D White Cement (g) 1180.00 472.00 472.00 472.00 531.00 ClinkerReduction (%) 0% 60% 60% 60% 55% GGBFS (g) 0 472.00 472.00 472.00 531.00Fine limestone powder (g) 0 236.00 118.00 0 0 Fine recycled glass (g) 00 118.00 0 0 Type S lime (g) 0 0 0 23.60 11.80 Coarse limestone sand (g)590.00 554.60 554.60 666.70 601.80 Medium limestone sand (g) 497.81467.94 467.94 562.53 507.77 Marble White 80 (g) 313.44 294.63 294.63460.38 415.29 PVA fiber (g) 6.50 6.50 6.50 0 0 Latex adhesive (g) 36.8836.88 36.88 30.24 23.63 Superplasticizer (ml) 2.2 2.2 2.2 2.2 4.0Viscosity modifying agent (g) 0.2 0.2 0.2 0.2 0.2 Water (g) 424.06424.06 424.06 354.73 385.90  3-day (psi/MPa) 6415/44.2 4883/33.74240/29.2 5132/35.4 6685/46.1  7-day (psi/MPa) 7488/51.6 6030/41.65910/40.7 7255/50.0 7793/53.7 28-day (psi/MPa) 8660/59.7 7410/51.18145/56.2 7925/54.6 10230/70.5 

As is readily apparent, by using GGBFS, limestone powder and/or Type Slime, all of which cost substantially less than white cement, cast stonemixes with clinker reductions of 55-60% were made having adequatestrength. Mixes 104A-104C had 60% clinker reduction and were comparablein strength (only slightly lower) compared to control Mix 104. Mix 104Dhad 55% clinker reduction and substantially higher strength at each of 3days, 7 days and 28 days compared to control Mix 104.

TABLE 22 Components/Compressive Example (Mix ID) Strength 104E 104F 104G104H 104I White Cement (g) 525.69 534.22 525.69 460.48 477.94 ClinkerReduction (%) 55.5% 54.7% 55.5% 61% 59.5% GGBFS (g) 525.69 534.22 525.69460.48 477.94 Type S lime (g) 10.62 5.37 10.62 25.79 18.38 Coarselimestone sand (g) 613.60 637.20 637.20 552.57 459.55 Medium limestonesand (g) 562.53 537.64 537.64 552.57 461.39 Marble White 80 (g) 354.18313.44 338.51 515.73 683.82 PVA fiber (g) 6.50 6.50 6.50 0 0 Latexadhesive (g) 23.20 30.54 29.87 29.47 31.25 Superplasticizer (ml) 2.7 2.62.6 3.0 2.6 Viscosity modifying agent (g) 0.1 0.1 0.0 0.05 0.05 Water(g) 383.66 385.90 381.66 338.38 365.44  3-day (psi/MPa) 6750/46.55875/40.5 3910/27.0 5695/39.3 7247/50.0  7-day (psi/MPa) 7465/51.58383/57.8 6757/46.6 8360/57.6 8475/58.4 28-day (psi/MPa) 8727/60.28935/61.6 10135/69.9  9700/66.9 9677/66.7

Mixes 104E-104I demonstrate that substituting between 54.7% and 61% ofthe white cement with GGBFS, an additional portion of Marble White 80,and Type S lime, all of which cost substantially less than white cement,yielded cast stone mixes with comparable to significantly higherstrength, particularly at 7 and 28 days, compared to control Mix 104.

Working Examples—GFRC

Glass fiber reinforced concrete (GFRC) mixes were made based on acommercial GFRC mix design that used Portland White Cement, threedifferently sized silica sand or coarse limestone powder aggregates(Wedron #530 medium silica sand, Scott #730 fine silica sand, and MarbleWhite 80 fine limestone aggregate/coarse limestone powder), latexadhesive to bond to polystyrene foam, glass fibers to increasetoughness, superplasticizer to maintain low water to cement ratio (i.e.,w/c=0.27), and viscosity modifying agent (cellulosic either) to preventsegregation and clogging of a GFRC nozzle. Mix 110 was a mortar mixderived from the commercial GFRC mix, used white cement as solecementitious binder, and is the control mix. Mixes 110A-110D weredesigned by the inventor to provide a similarly commercially acceptableGFRC mix but with substantially reduced cement clinker content and lowercost (i.e., about 10-20% less expensive in material cost compared to thecommercial mix design).

White cement, aggregates, fiber, adhesive, superplasticizer, andviscosity modifying agent were provided by Tuscan Stoneworx, Lindon,Utah. GGBFS was white or off-white and purchased from Lehigh Cement,Stockton, Calif. A sample of fine pumice was provided by Hess Pumice,Malad, Id. Type S lime was purchased from Home Depot, Salt Lake City,Utah. Interground volcanic ash and limestone was prepared byintergrinding at Gebr. Pfieffer GmbH, Kaiserslautern, Germany a volcanicash from a deposit in Stockton, Utah provided by Staker Parson, Ogden,Utah, with limestone granules provided by Pfeiffer.

TABLE 23 Components/Compressive Example (Mix ID) Strength 110 110A 110B110C 110D White Cement (g) 1344.58 615.42 553.56 553.56 553.56 ClinkerReduction (%) 0% 54.2% 58.8% 58.8% 58.8% GGBFS (g) 0 615.42 553.56553.56 553.56 Fine pumice (g) 0 0 123.70 0 0 Interground VA + LS (g) 0 00 123.70 0 Fly ash (g) 0 0 0 0 123.70 Type S lime (g) 0 6.19 6.19 6.196.19 Medium silica sand (g) 426.33 447.65 447.65 447.65 447.65 Finesilica sand (g) 623.10 654.25 654.25 654.25 654.25 Marble White 80 (g)196.77 267.60 240.06 242.02 267.60 Glass fiber (g) 98.38 98.38 98.3898.38 98.38 Latex adhesive (g) 32.79 30.17 30.17 30.17 30.17Superplasticizer (ml) 23 23 23 23 23 Viscosity modifying agent (g) 1.051.05 1.05 1.05 1.05 Water (g) 366.32 337.01 337.01 337.01 337.01  3-day(psi/MPa) 7385/50.9 7337/50.6  8540/58.9  6937/47.8 6285/43.3  7-day(psi/MPa) 8235/56.8 9665/66.6 11565/79.7 11230/77.4 8225/56.7 28-day(psi/MPa) 9705/66.9 11755/81.2  12250/84.5 12862/88.7 10960/75.6 

Mixes 110A-110D show that clinker reductions of about 54-58% werepossible by substituting part of the white cement with GGBFS andincreasing the amount of Marble White 80 fine aggregate, which is acoarse limestone powder. Each of Mixes 110A-110D had comparable orgreater strength compared to control Mix 110. At 28 days, Mixes110A-110D all had significantly to substantially higher strength thanMix 110, but with less than half of the original amount of white cement.When initially cast, Mixes 110A-110D were less white than Mix 110.However, after curing and drying, they were almost indistinguishable inwhiteness. If a pigment were used, the final color of Mixes 110A-110Dwould likely be virtually, if not entirely, indistinguishable from Mix110.

TABLE 24 Components/Compressive Example (Mix ID) Strength 110E 110F 110G110H White Cement (g) 865.91 865.91 0 0 Type I/II OPC (g) 0 0 786.58786.58 Clinker Reduction (%) 35.6% 35.6% 41.5% 41.5% Calcined shale dust(g) 358.73 0 417.49 417.49 Fine pumice (g) 0 358.73 0 0 Type S lime (g)12.37 12.37 6.05 6.05 Medium silica sand (g) 447.65 447.65 447.65 447.65Fine silica sand (g) 654.25 654.25 654.25 654.25 Mineral fines (g)238.09 238.09 265.25 265.25 Glass fiber (g) 49.00 49.00 49.00 49.00Latex adhesive (g) 30.17 30.17 30.17 30.17 Superplasticizer (ml) 23 2323 23 Viscosity modifying agent (g) 0.75 0.75 0.5 0.5 Water (g) 337.01337.01 329.69 363.04  3-day (psi/MPa) 7042/48.5 6200/42.7 6630/45.74932/34.0  7-day (psi/MPa) 8005/55.2 8817/60.8 8405/57.9 6085/41.928-day (psi/MPa) 11557/79.7  10345/71.3  10212/70.4  7680/52.9

Mixes 110E and 110F show that clinker reductions of about 35.6% werepossible when using much less expensive calcined shale dust and quarryfines instead of GGBFS and Marble White 80. Color was more of a naturallimestone color when using calcined shale dust and quarry fines. Themolded cubes had a nice, natural look in the absence of added pigments.They also had strengths that were superior to those of Mix 110 andcomparable to those of Mixes 110A-11D.

Mixes 110G-110H were made using Type I/II OPC, which costs about half asmuch as white cement, and also very inexpensive calcined shale dust andquarry fines. Cost savings were greater than 25% compared to Mix 110,although cement binder costs were reduced by more than 65%. Mixes110G-110H had strengths comparable or superior to those of Mix 110.

Examples—Concrete Washout Fines

Mortar mixes were prepared using concrete washout fines. A controlmortar mix made was manufactured using a silica sand and Portland cementfrom Home Depot in Salt Lake City, Utah. The cement was manufactured byAsh Grove and appears to be poor quality as compared to previousPortland cements obtained from the same Home Depot in Salt Lake City,Utah but manufactured by Holcim. While the strength was lower thanprevious control mortars made using different Portland cement, itprovided a baseline against which other mixes were compared. The mortarmixes were cast into 2 inch molds, cured, and tested by CMTLaboratories.

TABLE 25 Components/Compressive Example (Mix ID) Strength Control WF-1WF-2 WF-3 WF-4 Ash Grove Cement (g) 500 350 375 350 300 Class F fly ash(g) 0 100 62.5 75 100 Washout Fines (Ready 0 125 0 0 0 Made) WashoutFines (Delta) 0 0 125 150 200 Low range water reducer 0 0.5 0 0 0 (ml)Superplasticizer (ml) 0 0 1 2 4 Water (g) 242 242 242 242 242 SilicaSand (g) 1375 1238 1283.5 1265.5 1228.8  3-day (psi) 2552 2015 3635 34502475  7-day (psi) 4135 3185 4520 4350 3320 28-day (psi) 4405 1078 51955235 4365

Concrete mixes were prepared using concrete washout fines and Portlandcement from Home Depot in Salt Lake City, Utah. The mortar mixes werecast into 4×8 inch cylinder molds, cured, and tested by CMTLaboratories.

TABLE 26 Components/Compressive Example (Mix ID) Strength WF-5 WF-6 WF-7WF-8 Ash Grove Cement (lb/yd³) 501 467.6 450 400.01 Class F fly ash(lb/yd³) 100.2 0 90 100 Shale Dust (lb/yd³) 0 133.6 0 0 Washout Fines(Ready Made) 200.4 233.8 200.4 250 (lb/yd³) Coarse Aggregate (lb/yd³)1675 1700 1750 1750 Sand (lb/yd³) 1028 980 1075 1055 Low range waterreducer (oz/yd³) 27.05 28.06 18.90 20 Superplasticizer (oz/yd³) 0 0 0 0Air Entraining Agent (oz/yd³) 7.52 5.85 5.40 5.70 Water 293.92 293.92270 270  3-day (psi) 1680 2030 2390 2940  7-day (psi) 3075 3350 28503460  28-day (psi) 3940 4210 3640 4130  91-day 4430 4965 n/a n/a 182-dayn/a 5200 n/a n/a

Prophetic Examples 1

Any of the foregoing Examples is modified so that one more of thecomponents is altered by ±20%, ±18%, ±16%, ±14%, ±12%, ±10%, 8%, ±6%,±5%, ±4%, ±3%, ±2%, ±1.5%, ±1%, or 0.5%. The compositions have strengthsand other properties comparable to the corresponding Examples modified.

Prophetic Examples 2

Any of the foregoing Examples is modified so that one more of the ratios(w/c, w/cm, or w/p) is altered by ±20%, ±18%, ±16%, ±14%, ±12%, ±10%,8%, ±6%, ±5%, ±4%, ±3%, ±2%, ±1.5%, ±1%, or 0.5%. The compositions havestrengths and other properties comparable to the corresponding Examplesmodified.

Prophetic Examples 3

Any of the foregoing Examples is modified by adding carbon dioxide (CO₂)to the freshly mixed cementitious mixture at a rate of about 0.5 toabout 10 pounds of CO₂ per cubic yard. This results in cementitiouscompositions having lower CO₂ footprint and higher earlier strength. Anexample process for injecting CO₂ into concrete is provided by CarbonCure Technologies, Inc., headquartered in Dartmouth, Nova Scotia,Canada, such as disclosed in U.S. Pat. Nos. 8,845,940, 9,108,883,9,376,345, 9,388,072, 9,492,945, 9,738,562, 9,758,437, 9,790,131,10,246,379, and 10,350,787, which are incorporated herein by reference.Another example process for injecting CO₂ into concrete is disclosed inU.S. Patent Publication No. US 2017/0341988 to Welker et al., which isincorporated by reference.

An example process for mixing CO₂ with concrete wash water prior tomixing into fresh concrete is disclosed in US Pat. Pub. No. 2019/0168416to Monkman et al., which is incorporated by reference. The process inMonkman et al. for mixing CO₂ with concrete wash water can be modifiedto mix CO₂ with wet or dried concrete washout fines in order topassivate alkaline values. Dried concrete washout fines can be mixedwith water prior to or while mixing with CO₂ to facilitate the reaction.

CO₂ can be added to the fresh cementitious mixture and/or premixed withconcrete washout fines, by sparging in CO₂ gas, adding carbonated water,and/or adding crushed dry ice. A fine CO₂ “snow” can be formed byexpressing compressed CO₂ from a nozzle and mixing the CO₂ snow into thecementitious mixture using known means. An example mixing vessel is acentral mixer or concrete mixing truck used to manufacture ready mixedconcrete. The CO₂ can be injected under pressure into a pressurized feedline for introducing one or more components into the mixing vessel. Inthe case where the cementitious mixture is made using concrete washoutfines, highly alkaline values in the washout fines can be passivated byreacting them with CO₂ (e.g., after, while, or before being introducedinto the mixing vessel).

The present invention may be embodied in other specific forms withoutdeparting from its spirit or essential characteristics. The describedembodiments are to be considered in all respects only as illustrativeand not restrictive. The scope of the invention is, therefore, indicatedby the appended claims rather than by the foregoing description. Allchanges which come within the meaning and range of equivalency of theclaims are to be embraced within their scope.

The invention claimed is:
 1. A concrete mix comprising mixture productsof: a hydraulic cement selected from the group consisting of ordinaryPortland cement (OPC) having a d10 below about 3 μm and a d90 betweenabout 35 μm and about 45 μm, alkali-activated cement, and geopolymercement; at least one of fine ground granulated blast furnace slag(GGBFS) having a D90 between about 15 μm and about 25 μm, fly ash, ornatural pozzolan; mineral fines having a D90 between about 40 μm andabout 300 μm; coarse aggregate; fine aggregate; and water.
 2. Theconcrete mix of claim 1, further comprising at least one of addedcalcium oxide, calcium hydroxide, or Type S lime.
 3. The concrete mix ofclaim 1, further comprising at least one of added calcium sulfateanhydrite, calcium sulfate hemihydrate, lithium sulfate, or calciumsulfate dihydrate.
 4. The concrete mix of claim 1, further comprising atleast one of a polycarboxylate ether superplasticizer, an amineactivator, or a calcium nitrate activator.
 5. The concrete mix of claim1, wherein the mineral fines are selected from the group consisting ofwaste aggregate particles or fines, waste or manufactured limestonefines, shale flue dust from manufacturing lightweight calcined shaleaggregates, granite fines, stone dust, rock dust, marble dust, minetailings, pulverized bottom ashes, pulverized metallurgical slags, wasteor pulverized shale from shale oil extraction, and waste or pulverizedsand from tar sand extraction.
 6. The concrete mix of claim 1, whereinthe mineral fines comprise at least one of ground recycled concrete orconcrete washout fines.
 7. A method of manufacturing hardened concrete,comprising: providing the concrete mix of claim 1 while freshly mixed;placing the freshly mixed concrete mix into a shape and/or a mold; andallowing the concrete mix to harden.
 8. The method of claim 7, whereinthe mineral fines comprise concrete washout fines.
 9. The method ofclaim 7, further comprising adding at least one of calcium oxide,calcium hydroxide, or Type S lime to the concrete mix.
 10. The method ofclaim 7, further comprising adding at least one of calcium sulfateanhydrite, calcium sulfate hemihydrate, lithium sulfate, or calciumsulfate dihydrate to the concrete mix.
 11. The method of claim 7,wherein the mineral fines are selected from the group consisting ofwaste aggregate particles or fines, waste or manufactured limestonefines, shale flue dust from manufacturing lightweight calcined shaleaggregates, granite fines, stone dust, rock dust, marble dust, minetailings, pulverized bottom ashes, pulverized metallurgical slags, wasteor pulverized shale from shale oil extraction, and waste or pulverizedsand from tar sand extraction.
 12. The method of claim 7, wherein themineral fines comprise ground recycled concrete.
 13. A concrete mixcomprising mixture products of: a hydraulic cement selected from thegroup consisting of ordinary Portland cement (OPC) having a D10 belowabout 3 μm and a D90 between about 35 μm and about 45, alkali-activatedcement, and geopolymer cement; a fine pozzolanically reactivesupplementary cementitious material having a D90 less than about 25 μmselected from the group consisting of ground granulated blast furnaceslag (GGBFS), fine fly ash, ultrafine fly ash, silica fume, groundglass, and natural pozzolan; mineral fines having a D90 between about 40μm and about 300 μm; coarse aggregate; fine aggregate; and water. 14.The concrete mix of claim 13, wherein the mineral fines are selectedfrom the group consisting of waste aggregate particles or fines, wasteor manufactured limestone fines, shale flue dust from manufacturinglightweight calcined shale aggregates, granite fines, stone dust, rockdust, marble dust, mine tailings, pulverized bottom ashes, pulverizedmetallurgical slags, waste or pulverized shale from shale oilextraction, and waste or pulverized sand from tar sand extraction. 15.The concrete mix of claim 13, further comprising at least one of addedcalcium oxide, calcium hydroxide, Type S lime, calcium sulfateanhydrite, calcium sulfate hemihydrate, lithium sulfate, calcium sulfatedihydrate, or carbon dioxide.
 16. The concrete mix of claim 13, whereinthe mineral fines comprise concrete washout fines.
 17. A concrete mixcomprising mixture products of: a hydraulic cement selected from thegroup consisting of ordinary Portland cement (OPC) having a d10 belowabout 3 μm and a d90 between about 35 μm and about 45 μm,alkali-activated cement, and geopolymer cement; at least one pozzolanselected from the group consisting of fine ground granulated blastfurnace slag (GGBFS) having a D90 between about 15 μm and about 25 μm,fly ash, natural pozzolan, or shale flue dust; mineral fines having aD90 between about 40 μm and about 300 μm selected from the groupconsisting of waste aggregate particles or fines, waste or manufacturedlimestone fines, granite fines, stone dust, rock dust, marble dust, minetailings, pulverized bottom ashes, pulverized metallurgical slags, wasteor pulverized shale from shale oil extraction, waste or pulverized sandfrom tar sand extraction, and concrete washout fines; coarse aggregate;fine aggregate; and water.
 18. The concrete mix of claim 17, furthercomprising at least one of added calcium oxide, calcium hydroxide, TypeS lime, calcium sulfate anhydrite, calcium sulfate hemihydrate, lithiumsulfate, calcium sulfate dihydrate, or carbon dioxide.
 19. The concretemix of claim 17, wherein the mineral fines comprise concrete washoutfines.
 20. The concrete mix of claim 17, wherein the mineral finescomprise ground recycled concrete.